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TW201245058A - Glass substrate for flat panel glass - Google Patents

Glass substrate for flat panel glass Download PDF

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Publication number
TW201245058A
TW201245058A TW101120352A TW101120352A TW201245058A TW 201245058 A TW201245058 A TW 201245058A TW 101120352 A TW101120352 A TW 101120352A TW 101120352 A TW101120352 A TW 101120352A TW 201245058 A TW201245058 A TW 201245058A
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TW
Taiwan
Prior art keywords
glass substrate
flat panel
glass
panel display
supply step
Prior art date
Application number
TW101120352A
Other languages
Chinese (zh)
Other versions
TWI473770B (en
Inventor
Satoshi Takeda
Shirou Tanii
Seiji Higashi
Ryoji Akiyama
Original Assignee
Asahi Glass Co Ltd
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Publication of TW201245058A publication Critical patent/TW201245058A/en
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Publication of TWI473770B publication Critical patent/TWI473770B/en

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    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/22—Surface treatment of glass, not in the form of fibres or filaments, by coating with other inorganic material
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
    • C03B18/00—Shaping glass in contact with the surface of a liquid
    • C03B18/02—Forming sheets
    • C03B18/14—Changing the surface of the glass ribbon, e.g. roughening
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C21/00—Treatment of glass, not in the form of fibres or filaments, by diffusing ions or metals in the surface
    • C03C21/007—Treatment of glass, not in the form of fibres or filaments, by diffusing ions or metals in the surface in gaseous phase
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C3/00—Glass compositions
    • C03C3/04—Glass compositions containing silica
    • C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
    • C03C3/078—Glass compositions containing silica with 40% to 90% silica, by weight containing an oxide of a divalent metal, e.g. an oxide of zinc
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C3/00—Glass compositions
    • C03C3/04—Glass compositions containing silica
    • C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
    • C03C3/083—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C3/00—Glass compositions
    • C03C3/04—Glass compositions containing silica
    • C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
    • C03C3/083—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound
    • C03C3/085—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound containing an oxide of a divalent metal
    • C03C3/087—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound containing an oxide of a divalent metal containing calcium oxide, e.g. common sheet or container glass
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • H01J11/00—Gas-filled discharge tubes with alternating current induction of the discharge, e.g. alternating current plasma display panels [AC-PDP]; Gas-filled discharge tubes without any main electrode inside the vessel; Gas-filled discharge tubes with at least one main electrode outside the vessel
    • H01J11/20—Constructional details
    • H01J11/34—Vessels, containers or parts thereof, e.g. substrates
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • H01J9/00—Apparatus or processes specially adapted for the manufacture, installation, removal, maintenance of electric discharge tubes, discharge lamps, or parts thereof; Recovery of material from discharge tubes or lamps
    • H01J9/24—Manufacture or joining of vessels, leading-in conductors or bases
    • H01J9/241—Manufacture or joining of vessels, leading-in conductors or bases the vessel being for a flat panel display
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C2217/00—Coatings on glass
    • C03C2217/20—Materials for coating a single layer on glass
    • C03C2217/28—Other inorganic materials
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C2217/00—Coatings on glass
    • C03C2217/20—Materials for coating a single layer on glass
    • C03C2217/28—Other inorganic materials
    • C03C2217/283—Borides, phosphides
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C2218/00—Methods for coating glass
    • C03C2218/30—Aspects of methods for coating glass not covered above
    • C03C2218/355—Temporary coating
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • H01J2211/00—Plasma display panels with alternate current induction of the discharge, e.g. AC-PDPs
    • H01J2211/20—Constructional details
    • H01J2211/34—Vessels, containers or parts thereof, e.g. substrates
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P40/00—Technologies relating to the processing of minerals
    • Y02P40/50—Glass production, e.g. reusing waste heat during processing or shaping
    • Y02P40/57—Improving the yield, e-g- reduction of reject rates

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Geochemistry & Mineralogy (AREA)
  • General Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Plasma & Fusion (AREA)
  • Manufacturing & Machinery (AREA)
  • Glass Compositions (AREA)
  • Surface Treatment Of Glass (AREA)
  • Gas-Filled Discharge Tubes (AREA)

Abstract

A process for producing a glass substrate for flat panel glasses which retains satisfactory marring resistance and can be prevented from suffering colloidal-silver coloring; and a glass substrate for flat panel glasses which is obtained by the process. The process produces a glass substrate for flat panel glasses by the float method. It comprises a forming step in which a molten glass is formed on molten tin into a glass substrate and an annealing step in which the glass substrate formed in the forming step is annealed. The process further comprises a first supply step in which an inorganic substance containing an alkali metal is blown against that surface of the glass substrate which was in contact with the molten tin and a second supply step in which after the first supply step, SO2 gas is blown against that surface of the glass substrate which was in contact with the molten tin.

Description

201245058 六、發明說明： 【發明所屬之技術領域】 本發明係關於一種平面面板顯示器用玻璃基板之製造方 法0 【先前技術】 近年來，平板顯示器，尤其是作為薄型平板型氣體放電 顯示面板之一種之電漿顯示面板（以下，亦稱為Γ PDP， plasma display panel」）作為薄型且大型之平板型彩色顯示 裝置而備受關注。 PDP藉由正面玻璃基板、背面玻璃基板及障壁而區劃形 成單元’並於該單元中產生電漿放電，藉此使單元内壁之 螢光體層發光，形成圖像。 一般而言，PDP之正面玻璃基板及背面玻璃基板係使用 易於使玻璃基板大型化、且平坦性及均質性優異之浮法玻 璃’即，利用浮式法而於溶融錫上形成之玻璃基板。 又，於PDP中所使用之玻璃基板之未與溶融錫接觸之侧 的表面（以下’亦稱為「頂面」）形成包含IT〇(indium Un oxide ’氧化銦錫）之透明電極，並於其上利用網版印刷法 塗佈銀漿後於520〜600°C下加以燒成而形成銀電極。 然而’其存在如下問題：於對銀漿加以燒成而形成銀電 極時，玻璃基板顏色發黃，PDP彩色顯示之品質下降，具 體而言’顯示白色之畫面於銀電極周邊略帶黃色，或者顯 示藍色之畫面的亮度下降。 一般認為上述顏色發黃現象係因膠體之發色而引起的， £ 164689.doc 201245058 忒膠體係於形成銀電極時’自正面玻璃基板之頂面擴散至 内2部（表面層）之銀離子（Ag+)藉由存在於表面層之Fe2+、201245058 VI. Description of the Invention: [Technical Field] The present invention relates to a method for manufacturing a glass substrate for a flat panel display. [Prior Art] In recent years, flat panel displays, especially as a thin flat type gas discharge display panel The plasma display panel (hereinafter also referred to as "PDP, plasma display panel") has attracted attention as a thin and large flat type color display device. The PDP divides the cell by the front glass substrate, the back glass substrate, and the barrier ribs, and generates a plasma discharge in the cell, thereby causing the phosphor layer on the inner wall of the cell to emit light to form an image. In the front glass substrate and the rear glass substrate of the PDP, a float glass which is easy to increase the size of the glass substrate and which is excellent in flatness and homogeneity, that is, a glass substrate which is formed on the molten tin by a floating method, is used. Further, a surface of the glass substrate used in the PDP that is not in contact with the molten tin (hereinafter referred to as "top surface") forms a transparent electrode including IT〇 (indium Un oxide). The silver paste was applied thereon by screen printing, and then fired at 520 to 600 ° C to form a silver electrode. However, there is a problem in that when the silver paste is fired to form a silver electrode, the color of the glass substrate is yellow, and the quality of the PDP color display is lowered. Specifically, the image showing white is slightly yellow around the silver electrode, or The brightness of the blue screen is reduced. It is generally believed that the yellowing of the above color is caused by the color of the colloid. £ 164689.doc 201245058 The tantalum system diffuses from the top surface of the front glass substrate to the silver ions of the inner two (surface layer) when the silver electrode is formed. (Ag+) by Fe2+ present in the surface layer,

Sn等而還原成零價之Ago,藉由該Ag0凝集而生成者（例 如，參照專利文獻1及2)。 另一方面，對於以PDP為代表之利用浮式法而製造之玻 璃基板之與溶融錫浴中的溶融錫接觸之側的表面（以下， 亦稱為「底面」），必須防止其在離開溶融錫浴後藉由滾 筒而搬送時產生之傷痕。為了達成該目的，已知悉如下方 法：藉由喷附二氧化硫（S〇2氣體），使其與玻璃中所存在 之鹼金屬（例如’鈉等）或鹼土金屬（例如，鈣等）發生反 應，於玻璃基板之表面形成硫酸鈉，使其作為保護膜而發 揮作用，來防止傷痕之產生（例如，參照專利文獻3及非專 利文獻1等）。 [專利文獻1]日本專利特開平1〇·255669號公報 [專利文獻2]日本專利特開2005-55669號公報 [專利文獻3]國際公開第2002/051767號小冊子 [非專利文獻1] U. Senturk etc, J. Non-Cryst. Solids，第 222卷，p.160(1997) 【發明内容】 [發明所欲解決之問題] 本發明者進一步就上述Ag膠體發色之原因進行反覆潛心 研究’結果發現，為形成保護被膜而向玻璃基板之底面所 喷附之S02氣體亦流入至玻璃基板頂面係一個重大原因。 即，已弄明如下情況：由於S02氣體流入至頂面，故而 164689.doc 201245058 於頂面亦形成保護被膜，與此同時，H+自頂面滲入至玻璃 基板之内部（表面層），其結果使得於銀電極形成時，Ag+ 易於進入至表面層。具體而言，已弄明如下情況：s〇2氣 體與環境氣體中之水蒸汽發生反應而形成 H2S〇3(H20+S〇2—^H2S〇3) ’藉由表面層所存在之Na+及H+ 之取代反應（2Na++H2S〇3~^2H++Na2S〇3)，H+滲入至玻璃基 板之表面層’再藉由該H+與Ag+之交換反應，而於銀電極 形成時’使Ag易於進入至表面層。 另一方面，如上所述，自形成玻璃保護被膜來防止玻璃 基板傷痕產生之觀點來考慮，向玻璃基板之底面喷附s〇2 氣體之操作本身’在一定程度上為必需之處理。 此處，本發明之目的在於，提供一種可維持良好之耐傷 性，並且防止Ag膠體發色之平面面板顯示器用玻璃基板之 製造方法、以及利用該製造方法而獲得之平面面板顯示器 用玻璃基板。 [解決問題之技術手段] 本發明者為了達成上述目的而潛心研究，結果發現，於 利用浮式法之製造步驟中，藉由將含有鹼金屬之無機物質 向玻璃基板之底面及/或頂面喷附而供給鹼金屬，繼而向 底面喷附S〇2氣體’可維持良好之耐傷性，並且防止Ag膠 體發色，從而完成本發明。 即，本發明提供以下（丨）〜（17)。 (1)種平面面板顯示器用玻璃基板之製造方法，其係 和用孕式法來製造平面面板顯示器用玻璃基板者； 164689.doc 201245058 其具備：成形步驟’將熔融玻璃於熔融錫上成形為玻璃 基板；以及徐冷步驟，使藉由上述成形步驟而成形之上述 玻璃基板徐冷；且 具備：第1供給步驟，向上述玻璃基板之與上述熔融錫 接觸之側的表面喷附含有驗金屬之無機物質；以及第2供 給步驟，於上述第1供給步驟之後，向上述玻璃基板之與 上述熔融錫接觸之側的表面噴附S02氣體。 (2) —種平面面板顯示器用玻璃基板之製造方法，其係 利用浮式法來製造平面面板顯示器用玻璃基板者； 其具備：成形步驟’將熔融玻璃於熔融錫上成形為玻璃 基板；以及徐冷步驟’使藉由上述成形步驟而成形之上述 玻璃基板徐冷；且 具備：第1供給步驟，向上述玻璃基板之未與上述熔融 錫接觸之側的表面喷附含有鹼金屬之無機物質；以及第2 供給步驟’於上述第1供給步驟之後，向上述玻璃基板之 與上述熔融錫接觸之側的表面喷附S〇2氣體。 (3) 如上述（1)或（2)之平面面板顯示器用玻璃基板之製造 方法，其中上述第1供給步驟係於上述成形步驟與上述徐 冷步驟之間實施。 (4) 如上述（1)或（2)之平面面板顯示器用玻璃基板之製造 方法’其中上述第1供給步驟係於上述玻璃基板之破璃轉 移點± 1 〇〇°C之範圍的溫度下實施。 (5) 如上述（1)或（2)之平面面板顯示器用玻璃基板之製造 方法’其中上述第1供給步驟係於550〜750。〇下實施。 164689.doc 201245058 (6) 如上述⑴至（5)中任—項之平面面板顯示器用玻璃基 板之製以方法，其中上述苐2供給步驟係於上述成形步驟 與上述徐冷步驟之間實施。 (7) 如上述⑴至（5)中任_項之平面面板顯示器用玻璃基 板之袅：^方法，其中上述第2供給步驟係於上述玻璃基板 之玻璃轉移點±100。(：之範圍的溫度下實施。 (8) 如上述（”至^)中任一項之平面面板顯示器用玻璃基 板之衣k方法，其中上述第2供給步驟係於55〇〜75〇它下實 施。 (9) 一種平面面板顯示器用玻璃基板之製造方法，其係 利用洋式法來製造平面面板顯示器用玻璃基板者； 其具備成形步驟，將熔融玻璃於熔融錫上成形為玻璃基 板；且 具備：第1供給步驟，於550〜75CTC下向上述玻璃基板之 與上述熔融錫接觸之側的表面噴附含有鹼金屬之無機物 質；以及第2供給步驟，於上述第丨供給步驟之後，於 5 50〜750 C下向上述玻璃基板之與上述熔融錫接觸之側的 表面喷附S02氣體。 (10) —種平面面板顯示器用玻璃基板之製造方法，其 係利用浮式法來製造平面面板顯示器用玻璃基板者； 其具備成形步驟，將熔融玻璃於熔融錫上成形為玻璃基 板；且 具備：第1供給步驟，於550〜750。〇下向上述玻璃基板之 未與上述熔融錫接觸之側的表面喷附含有鹼金屬之無機物 164689.doc .7. ^ 201245058 質，以及第2供給步驟，於上述第丨供給步驟之後，於 550〜750 C下向上述玻璃基板之與上述溶融錫接觸之側的 表面喷附so2氣體。 (11) 如上述（1)至（10)中任一項之平面面板顯示器用玻璃 基板之製造方法，其t上述含有鹼金屬之無機物質含有鈉 及硼。 (12) 如上述（11)之平面面板顯示器用玻璃基板之製造方 法’其中上述含有鹼金屬之無機物質為四硼酸鈉。 (13) —種平面面板顯示器用玻璃基板，其係利用上述 (11)或（I2)之製造方法而製造。 (14) 一種平面面板顯示器用玻璃基板，其係利用上述 (11)或（12)之製造方法而製造者， 上述玻璃基板以氧化物為基準且以質量百分率表示，含 有：The Ago which is reduced to zero by Sn or the like is generated by the aggregation of Ag0 (for example, refer to Patent Documents 1 and 2). On the other hand, the surface of the glass substrate produced by the floating method represented by the PDP and the side of the molten tin in the molten tin bath (hereinafter, also referred to as "bottom surface") must be prevented from leaving the molten metal. Scars generated when transported by a roller after a tin bath. In order to achieve the object, a method is known in which a sulfur dioxide (S〇2 gas) is sprayed to react with an alkali metal (for example, 'sodium or the like) or an alkaline earth metal (for example, calcium, etc.) present in the glass. Sodium sulfate is formed on the surface of the glass substrate to act as a protective film to prevent the occurrence of scratches (for example, refer to Patent Document 3 and Non-Patent Document 1). [Patent Document 1] Japanese Laid-Open Patent Publication No. 2005-55669 [Patent Document 3] International Publication No. 2002/051767 [Non-Patent Document 1] U. Senturk etc, J. Non-Cryst. Solids, Vol. 222, p. 160 (1997) [Disclosure] [The problem to be solved by the invention] The present inventors further studied the cause of the above-mentioned Ag colloid color development. As a result, it was found that the SO 2 gas sprayed onto the bottom surface of the glass substrate to form the protective film also flowed into the top surface of the glass substrate for a major reason. That is, it has been found that since the S02 gas flows into the top surface, 164689.doc 201245058 forms a protective film on the top surface, and at the same time, H+ penetrates into the inside (surface layer) of the glass substrate from the top surface, and as a result, This makes it easy for Ag+ to enter the surface layer when the silver electrode is formed. Specifically, it has been found that the s〇2 gas reacts with the water vapor in the ambient gas to form H2S〇3 (H20+S〇2—^H2S〇3)' by the Na+ present in the surface layer and H+ substitution reaction (2Na++H2S〇3~^2H++Na2S〇3), H+ infiltrates into the surface layer of the glass substrate, and then exchanges the H+ and Ag+, and when the silver electrode is formed, 'Ag Easy access to the surface layer. On the other hand, as described above, from the viewpoint of forming a glass protective film to prevent the occurrence of a flaw in the glass substrate, the operation of attaching the gas of s〇2 to the bottom surface of the glass substrate is a necessary treatment to some extent. Here, an object of the present invention is to provide a method for producing a glass substrate for a flat panel display which can maintain good scratch resistance and prevent color development of an Ag colloid, and a glass substrate for a flat panel display obtained by the method. [Means for Solving the Problems] The inventors of the present invention have diligently studied in order to achieve the above object, and as a result, found that in the manufacturing step by the floating method, the inorganic substance containing an alkali metal is applied to the bottom surface and/or the top surface of the glass substrate. The injection of the alkali metal and subsequent spraying of the S 2 gas to the bottom surface maintains good scratch resistance and prevents the Ag colloid from developing color, thereby completing the present invention. That is, the present invention provides the following (丨) to (17). (1) A method for producing a glass substrate for a flat panel display, and a method for producing a glass substrate for a flat panel display by a pregnancy method; 164689.doc 201245058 comprising: forming step of forming molten glass on molten tin a glass substrate; and a cooling step of causing the glass substrate formed by the forming step to be cold-cooled; and a first supplying step of spraying a metal containing the metal on a surface of the glass substrate contacting the molten tin In the second supply step, after the first supply step, the SO 2 gas is sprayed onto the surface of the glass substrate on the side in contact with the molten tin. (2) A method for producing a glass substrate for a flat panel display, which is a glass substrate for a flat panel display by a floating method; and a molding step of: forming a molten glass on a molten tin into a glass substrate; The cold cooling step 'cools the glass substrate formed by the forming step; and includes a first supply step of spraying an alkali metal-containing inorganic substance onto a surface of the glass substrate that is not in contact with the molten tin And the second supply step 'after the first supply step, the S〇2 gas is sprayed onto the surface of the glass substrate on the side in contact with the molten tin. (3) The method of producing a glass substrate for a flat panel display according to (1) or (2), wherein the first supply step is performed between the forming step and the quenching step. (4) The method for producing a glass substrate for a flat panel display according to the above (1) or (2) wherein the first supply step is at a temperature within a range of ± 1 〇〇 ° C of the glass transition point of the glass substrate Implementation. (5) The method for producing a glass substrate for a flat panel display according to (1) or (2) above, wherein the first supply step is 550 to 750. Implemented under your Majesty. The method for producing a glass substrate for a flat panel display according to any one of the above items (1) to (5), wherein the 苐2 supply step is performed between the forming step and the quenching step. (7) The method of the glass substrate for a flat panel display according to any of the above (1) to (5) wherein the second supply step is a glass transition point of the glass substrate of ±100. (8) The method of coating a glass substrate for a flat panel display according to any one of the above (the above), wherein the second supply step is 55 〇 75 75 75 (9) A method for producing a glass substrate for a flat panel display, which is a glass substrate for a flat panel display by a foreign method; and a molding step for forming a molten glass on a molten tin into a glass substrate; a first supply step of ejecting an alkali metal-containing inorganic substance onto a surface of the glass substrate on the side in contact with the molten tin at 550 to 75 CTC; and a second supply step, after the second supply step, at 5 50 to 750 C, the SO 2 gas is sprayed onto the surface of the glass substrate on the side in contact with the molten tin. (10) A method for producing a glass substrate for a flat panel display, which is a flat panel display manufactured by a floating method A glass substrate; comprising: a molding step of molding molten glass on molten tin into a glass substrate; and comprising: a first supply step of 550 to 750. The surface of the glass substrate on the side not in contact with the molten tin is sprayed with an alkali metal-containing inorganic substance 164689.doc.7. ^ 201245058, and a second supply step, after the above-mentioned third supply step, at 550 to 750 C The method of producing a glass substrate for a flat panel display according to any one of the above (1) to (10), wherein the above-mentioned glass substrate is coated with a method of producing a glass substrate for a flat panel display. (12) The method for producing a glass substrate for a flat panel display according to the above (11), wherein the inorganic substance containing an alkali metal is sodium tetraborate. (13) A flat panel The glass substrate for a display is manufactured by the manufacturing method of the above (11) or (I2). (14) A glass substrate for a flat panel display, which is manufactured by the manufacturing method of the above (11) or (12). The glass substrate is expressed by mass percentage based on an oxide and contains:

Si02 : 45-70%，Si02 : 45-70%,

Al2〇3 : 〇〜20%，Al2〇3 : 〇~20%,

CaO : 〇〜20%，CaO : 〇~20%,

Zr02 : 〇〜13%， 驗土金屬氧化物成分之合計量：5〜4〇%， 驗金屬氧化物成分之合計量：5〜30%， 上述玻璃基板之與上述溶融錫接觸之側的表面及/或上 述玻璃基板之未與上述溶融錫接觸之側的表面之平均硼濃 度為2〜6原子％，且硼向上述玻璃基板之内部之擴散深度 為 20〜80 nm 〇 164689.doc 201245058 (15) 如上述（14)之平面面板顯示器用玻璃基板，其中自 上述玻璃基板之未與上述溶融錫接觸之側的表面起至〇.】 μηι之深度為止之平均η原子濃度為25莫耳％以下。 (16) -種平面面板顯示器用玻璃基板，其係利用上述 (11)或（I2)之製造方法而製造者， 上述玻璃基板以氧化物為基準且以質量百分率表厂、人 有： 、 不’ 3Zr02 : 〇~13%, the total amount of the earth metal oxide component: 5 to 4%, the total amount of the metal oxide component: 5 to 30%, the surface of the glass substrate on the side in contact with the molten tin And/or the surface of the glass substrate on the side not in contact with the molten tin has an average boron concentration of 2 to 6 atom%, and the diffusion depth of boron to the inside of the glass substrate is 20 to 80 nm. 〇164689.doc 201245058 ( [15] The glass substrate for a flat panel display according to (14) above, wherein an average η atomic concentration of the surface of the glass substrate from the side not in contact with the molten tin to a depth of η. the following. (16) A glass substrate for a flat panel display, which is manufactured by the above-described (11) or (I2) manufacturing method, wherein the glass substrate is based on an oxide and is expressed by a mass percentage: ' 3

Si02 : 45〜70%，Si02: 45~70%,

Al2〇3 : 〇〜20%，Al2〇3 : 〇~20%,

CaO : 0〜20%，CaO : 0~20%,

Zr02 : 0〜13%， 鹼土金屬氧化物成分之合計量：5〜4〇%， 驗金屬氧化物成分之合計量：5〜3〇〇/。， 自上述玻璃基板之未邀！ w、# 、上述，合融錫接觸之側的表面起至 〇.1 μηι之深度為止之平均η原子濃度為25莫耳％以下。 (17) —種平面面板顯示器用诂掖 ^ 「益用玻璃基板，其以氧化物 基準且以質量百分率表示，含有： 馬Zr02 : 0 to 13%, the total amount of alkaline earth metal oxide components: 5 to 4%, the total amount of metal oxide components: 5 to 3 〇〇 /. , from the above glass substrate is not invited! w, #, and above, the average η atomic concentration of the surface on the side where the molten tin contacts is from the depth of 〇.1 μηι is 25 mol% or less. (17) — for flat panel display 诂掖 ^ "Used glass substrate, which is based on oxide and expressed in mass percent, contains:

Si02 : 45-70%，Si02 : 45-70%,

Al2〇3 : 〇〜20%，Al2〇3 : 〇~20%,

CaO : 〇〜20%，CaO : 〇~20%,

Zr02 : 0〜13%， 鹼土金屬氧化物成分之合計量：5〜4〇%， 鹼金屬氧化物成分之合計量：5〜3〇%， 且蝴自該 至少其中一表面之平均硼濃度為2〜6原子％ 164689.doc 201245058 表面向内部之擴散深度為20〜80 nm。 [發明之效果] 如以下所示，根據本發明，可提供一種可維持良好之耐 傷性，並且防止Ag膠體發色之平面面板顯示器用玻璃基板 之製造方法、以及利用該製造方法而獲得之平面面板顯示 器用玻璃基板。 又，本發明不僅適用於PDP，而且在表面場發射顯示器 [FED(Fleld Emission Display)]、表面傳導型電子發射顯示 器[SED(Surface_conduction Electron-emitter Display)]等之 中亦可維持良好之耐傷性，並且防止八8膠體發色，故而 亦適用於表面場發射顯示器、表面傳導型電子發射顯示器 等。 【實施方式】 以下’詳細說明本發明。 本發明之第1態樣之平面面板顯示器用玻璃基板之製造 方法（以下，亦稱為「本發明之第〗製造方法」）係利用浮式 法來製造平面面板顯示器用玻璃基板者； 其具備.成形步驟’將熔融玻璃於熔融錫上成形為玻璃 基板’以及徐冷步驟，使藉由上述成形步驟而成形之上述 玻璃基板徐冷；且 具備·第1供給步驟，向上述玻璃基板之與上述熔融錫 接觸之側的表面嘴附含有驗金屬之無機物質（以下，亦稱 為3驗金屬無機物質」）；以及第2供給步驟，於上述第 1供給步驟之後’向上述玻璃基板之與上述熔融錫接觸之 I64689.doc 201245058 側的表面，即，喷附有上述無機物質之表面喷附so2氣 體。 又，本發明之第2態樣之平面面板顯示器用玻璃基板之 製造方法（以下，亦稱為「本發明之第2製造方法」）係利用 浮式法來製造平面面板顯示器用玻璃基板者； 其具備：成形步驟，將溶融玻璃於溶融錫上成形為玻璃 基板；以及徐冷步驟，使藉由上述成形步驟而成形之上述 玻璃基板徐冷；且 具備.第1供給步驟，向上述玻璃基板之未與上述溶融 錫接觸之側的表面噴附含有鹼金屬之無機物質；以及第2 供步驟，於上述第丨供給步驟之後，向上述玻璃基板之 與上述溶融錫接觸之側的表面喷附s〇2氣體。 其次’詳細敍述本發明之第1製造方法及第2製造方法 (以下’若未特別註明，則將該等統稱為「本發明之製造 方法」）之成形步驟、徐冷步驟、第丨供給步驟及第2供給 步驟。 [成形步驟] 上述成形步驟係將熔融玻璃於熔融錫浴中之熔融錫上成 形為玻璃基板之步驟’為通常之浮式法之先前眾所周知的 步驟。 圖1係表示利用浮式法之玻璃製造線之一例的概念圖9 如圖1所不’於浮式法中’首先，於充滿熔融錫1之熔融 錫浴2之浴面上’自熔融窯3連續地流入熔融玻璃4，形成 玻璃帶。其次’使該玻璃帶沿著熔融錫浴2之浴面一邊漂 164689.doc i -11- 201245058 斤一邊前進，藉此使溫度降低並且使玻璃帶成形為板狀。 其後，將製成板狀之玻璃基板由引導輥5引導，以於長度 方向上連續之狀態搬運至徐冷爐6。 此處，於圖1中，上述成形步驟係將熔融玻璃4經由玻璃 帶直至成形為板狀為止之步驟。 於本發明中，與通常之浮式法相同，作為熔融錫浴2, 係使用包括由特殊耐火物蓋住金屬箱之内侧之錫浴爐以及 頂棚，用以防止錫氧化之密閉構造者。作為熔融錫浴内之 環境氣體，可使用包括氫氣及氮氣之混合氣體（氫氣之含 量為2〜10體積％)。 又’上述成形步驟之熔融錫浴中之溫度條件與通常之浮 式法相同，為600〜l〇5(TC，即，可將流入至熔融錫浴内之 熔融玻璃之溫度於上游側設為900〜l〇5〇°C，於下游側設為 600〜800°C。再者，該溫度通常藉由熔融玻璃之熱量來維 持，為了調節溫度，亦可使用加熱器或冷卻器。 本發明之製造方法係製造平面面板顯示器用玻璃基板之 方法’因此較好的是，成形於溶融錫上之玻璃基板為如下 組成，以氧化物為基準且以質量百分率表示，含有：Zr02 : 0 to 13%, the total amount of alkaline earth metal oxide components: 5 to 4% by weight, the total amount of alkali metal oxide components: 5 to 3 %, and the average boron concentration from at least one of the surfaces is 2~6 atom% 164689.doc 201245058 The depth of the surface to the inside is 20~80 nm. [Effects of the Invention] As described below, according to the present invention, it is possible to provide a method for producing a glass substrate for a flat panel display which can maintain good scratch resistance and prevent color development of an Ag colloid, and a plane obtained by the method. A glass substrate for a panel display. Moreover, the present invention is not only applicable to a PDP, but also maintains good scratch resistance in a surface field emission display [FED (Fleld Emission Display)], a surface conduction type electron emission display (SED (Surface_conduction Electron-emitter Display)], and the like. And to prevent the eight 8 colloid color, it is also suitable for surface field emission display, surface conduction type electron emission display and the like. [Embodiment] Hereinafter, the present invention will be described in detail. A method for producing a glass substrate for a flat panel display according to a first aspect of the present invention (hereinafter also referred to as "the manufacturing method of the present invention") is a method for manufacturing a glass substrate for a flat panel display by a floating method; a molding step of "molding molten glass on molten tin into a glass substrate" and a cooling step of causing the glass substrate formed by the molding step to be cold-cooled; and providing a first supply step to the glass substrate The surface nozzle on the side in contact with the molten tin is provided with an inorganic substance (hereinafter, also referred to as a "metal-inorganic substance"); and a second supply step, after the first supply step, to the glass substrate The surface of the above-mentioned molten tin contact I64689.doc 201245058 side, that is, the surface on which the above inorganic substance is sprayed, is sprayed with the so2 gas. Further, a method for producing a glass substrate for a flat panel display according to a second aspect of the present invention (hereinafter also referred to as "the second manufacturing method of the present invention") is a method for manufacturing a glass substrate for a flat panel display by a floating method; The method includes a molding step of forming a molten glass on a molten tin into a glass substrate, and a step of cooling to freeze the glass substrate formed by the molding step, and providing a first supply step to the glass substrate An inorganic substance containing an alkali metal is sprayed on a surface of the side not in contact with the molten tin; and a second supply step is performed on the surface of the glass substrate on the side in contact with the molten tin after the second supply step S〇2 gas. Next, the first manufacturing method and the second manufacturing method of the present invention (hereinafter, "the manufacturing method of the present invention will be collectively referred to as "the manufacturing method of the present invention" unless otherwise specified) will be described in detail. And a second supply step. [Molding step] The above-described forming step is a step of forming molten glass on molten tin in a molten tin bath into a glass substrate, which is a previously known step of the usual floating method. Fig. 1 is a view showing an example of a glass manufacturing line using a floating method. Fig. 9 is not in the floating method as shown in Fig. 1. First, a self-melting kiln on a bath surface of a molten tin bath 2 filled with molten tin 1. 3 continuously flows into the molten glass 4 to form a glass ribbon. Next, the glass ribbon was advanced along the bath surface of the molten tin bath 2 while 164689.doc i -11 - 201245058 kg was advanced, thereby lowering the temperature and forming the glass ribbon into a plate shape. Thereafter, the plate-shaped glass substrate is guided by the guide rolls 5, and is conveyed to the quenching furnace 6 in a state of being continuous in the longitudinal direction. Here, in Fig. 1, the forming step is a step of passing the molten glass 4 through a glass ribbon until it is formed into a plate shape. In the present invention, as in the conventional floating method, as the molten tin bath 2, a sealed structure in which a tin bath furnace and a ceiling including a special refractory cover the inside of the metal case are used to prevent oxidation of tin are used. As the ambient gas in the molten tin bath, a mixed gas containing hydrogen and nitrogen (hydrogen content of 2 to 10% by volume) can be used. Further, the temperature condition in the molten tin bath of the above-described forming step is 600 to 10 TC 5 (TC, that is, the temperature of the molten glass flowing into the molten tin bath can be set on the upstream side as in the usual floating method. 900~l〇5〇°C, 600~800°C on the downstream side. Further, the temperature is usually maintained by the heat of the molten glass, and a heater or a cooler may be used for adjusting the temperature. The manufacturing method is a method of manufacturing a glass substrate for a flat panel display. Therefore, it is preferable that the glass substrate formed on the molten tin has the following composition, and is expressed by mass percentage based on the oxide, and contains:

Si02 ： 45-70% > AI2O3 : 〜20%，Si02 : 45-70% > AI2O3 : ~20%,

CaO : 0〜20%，CaO : 0~20%,

Zr02 : 0〜13%， 驗土金屬氧化物成分之合計量：5〜40%， 驗金屬氧化物成分之合計量：5〜3 0%。 164689.doc 12· 201245058 於本發明中’更好的是，成形於溶融錫上之玻璃基板為 如下組成’以氧化物為基準且以質量百分率表示，含有：Zr02 : 0~13%, the total amount of soil oxide metal oxide components: 5~40%, the total amount of metal oxide components: 5~3 0%. 164689.doc 12· 201245058 In the present invention, it is more preferable that the glass substrate formed on the molten tin has the following composition, which is expressed by mass percentage based on the oxide, and contains:

Si02 : 50〜65%，Si02: 50~65%,

Al2〇3 : 〇〜15%，Al2〇3 : 〇~15%,

MgO : 〇〜15%，MgO : 〇~15%,

CaO ： 0-15% .CaO : 0-15% .

SrO : 〇〜20% ,SrO : 〇~20%

BaO . 〇〜20%，BaO . 〇~20%,

Zr02 : 0-13% > 驗土金屬氧化物成分之合計量：5〜4〇〇/0， 驗金屬氧化物成分之合計量：5〜3 0〇/〇。 又，於本發明中，更好的是，成形於溶融錫上之玻璃基 板為如下組成，以氧化物為基準且以質量百分率表示，含 有：Zr02 : 0-13% > The total amount of soil oxide metal oxide components: 5~4〇〇/0, the total amount of metal oxide components: 5~3 0〇/〇. Further, in the present invention, it is more preferable that the glass substrate formed on the molten tin has the following composition, expressed in terms of mass percentage based on the oxide, and contains:

Si02 : 50〜65%，Si02: 50~65%,

Al2〇3 : 2〜15%，Al2〇3: 2~15%,

MgO : 〇〜15%，MgO : 〇~15%,

CaO : 0-15%，CaO : 0-15%,

SrO ： 0-20% »SrO : 0-20% »

BaO : 〇〜20〇/〇，BaO : 〇~20〇/〇,

Zr〇2 · 0~6% 5 驗土金屬氧化物成分之合計量：1 〇〜3 0%， 驗金屬氧化物成分之合計量：6〜15%。 此外，於本發明中，更好的是，成形於溶融錫上之玻璃 164689.doc •13·Zr〇2 · 0~6% 5 The total amount of soil oxide metal components: 1 〇~3 0%, the total amount of metal oxide components: 6~15%. Further, in the present invention, it is more preferable that the glass formed on the molten tin is 164689.doc •13·

S 201245058 基板為如下組成’以氧化物為基準且以質量百分率表示， 含有：S 201245058 The substrate is of the following composition 'based on oxide and expressed in mass percent, containing:

Si〇2 . 52〜62%， AI2O3 . 5~12%，Si〇2 . 52~62%, AI2O3 . 5~12%,

MgO · 0~5% >MgO · 0~5% >

CaO : 3〜120/〇，CaO : 3~120/〇,

SrO : 4〜180/〇，SrO : 4~180/〇,

BaO : 0〜130/〇，BaO : 0~130/〇,

Zr02 : 0〜6%， 驗土金屬氧化物成分之合計量：15〜3 〇%， 驗金屬氧化物成分之合計量：6〜14%。 此外，又於本發明t，尤其好的是，成形於溶融錫上之 玻璃基板為如下組成’以氧化物為基準且以質量百分率表 示，含有：Zr02: 0~6%, the total amount of soil oxide metal oxide components: 15~3 〇%, the total amount of metal oxide components measured: 6~14%. Further, in the present invention t, it is particularly preferable that the glass substrate formed on the molten tin has the following composition 'as an oxide based on the mass percentage, and contains:

Si02 : 52〜62%，Si02: 52~62%,

Al2〇3 : 5~12%，Al2〇3 : 5~12%,

MgO : 0〜4%，MgO : 0~4%,

CaO : 3〜5.5%，CaO: 3~5.5%,

SrO : 6〜9%，SrO: 6 to 9%,

BaO : 0〜130/〇，BaO : 0~130/〇,

Zr02 : 0.2〜6%， 驗土金屬氧化物成分之合計量：1 7~27%， 驗金屬氧化物成分之合計量：7〜14%。 於本發明中’自強度及透過率之觀點來考慮，成形於溶 164689.doc •14- 201245058 融錫上之破璃基板之厚度較好的是1〜3 mm。 [徐冷步驟] 上述徐冷步驟係使藉由上述成形步驟而成形之上述玻璃 基板徐冷之步驟。 此處，於圖i中’上述徐冷步驟係’自將製成板狀之玻 璃基板由引導輥5引導開始’直至以於長度方向上連續之 狀態搬運至徐冷爐6中進行徐冷為止之步驟。 於本發明巾，作為徐冷爐，可使㈣itf之浮式法所使 用者相同的徐冷爐，為了控制溫度，亦可設置加熱器等。 又，上述徐冷步驟之徐冷爐之徐冷條件與通常之浮式法 相同，可於徐冷爐之入口處設為55〇〜75〇t，於 為200〜300。(：為止之溫度，溫度之下降速度可設為9〇。。土1〇 °C/m。 [第1供給步驟] 於本發明之第1製造方法中，上述W供給步驟係向上述 玻璃基板之底面噴附含鹼金屬無機物質而向該底面供給鹼 金屬之步驟（以下，亦稱為「第丨供給步驟（第i製造方 法）」）。 於第1供給步驟（第1製造方法）中，可提供一種平面面板 顯不器用玻璃基板之製造方法，其藉由使用含鹼金屬無機 物質而向上述玻璃基板之底面供給鹼金屬，可維持良好之 耐傷性，並且防止Ag膠體發色。 其原因可認為在於，藉由下述第2供給步驟而噴附之s〇2 氣體與供給至底面之鹼金屬優先反應，可防止該s〇2氣體 164689.doc -15· 201245058 流入至玻璃基板之頂面。 又’藉由使用含鹼金屬無機物質而將鹼金屬供給至上述 玻璃基板之底面’亦可抑制由鹼土金屬得來之硫酸鹽（例 如” 弓硫酸錄等）之生成，並且有效生成由驗金屬 知·來之硫酸鹽（例如，硫酸鈉等）之保護被膜，故而亦可實 現S〇2氣體使用量之減少。再者，硫酸鈣、硫酸锶等鹼土 金屬之硫酸鹽係難溶於水之難溶性物質，故而作為反應性 生物欠佳。 另一方面’於本發明之第2製造方法中，上述第1供給步 驟係向上述玻璃基板之頂面噴附含有鹼金屬之無機物質， 將驗金屬供給至該頂面之步驟（以下，亦稱為「第1供給步 驟（第2製造方法）」）。 於第1供給步驟（第2製造方法）中，可提供一種平面面板 顯不器用玻璃基板之製造方法，其藉由使用含鹼金屬無機 物質而向上述玻璃基板之頂面供給鹼金屬，可防止Ag膠體 發色。 此處’所謂含鹼金屬無機物質如上所述，係指含有鹼金 屬之無機物質，例如，含有鋰（Li)、鈉（Na)、鉀（K)、鉋 (Cs)等之無機物質即屬於此。 作為含有Na之無機物質，具體而言，例如可列舉： NaOH、Na2S、NaCl、NaF、NaBr、Nal、蘇打灰、 NaNH2、鈉节趟、NaBH4、NaCN、NaN03、Na2B407-10H2〇(四硼酸鈉十水合物）、Na2B4〇7、（C2H5)4BNa等，該 等可單獨使用1種，亦可併用2種以上。 164689.doc -16 201245058 作為含有κ之無機物質，具體而言，例如可列舉： KOH、KC1、KF、KBr、KI、KCN、k2C〇3、葡萄糖酸 鉀、KHF2、KN〇3、K2B4〇7_4H2〇(四硼酸鉀四水合物）、 K2B4〇7、KBF4等’該等可單獨使用！種，亦可併用2種以 上。 作為含有Cs之無機物質，具體而言，例如可列舉： CsOH、CsCl、CsF、CsBr、Csl、乙醯丙酮酸鉋、 HCOsCs、CsN〇3等，該等可單獨使用！種，亦可併用2種以 上。 根據以下所示之理由，含鹼金屬無機物質較好的是含有 Na之無機物質。 即，於本發明之第丨製造方法中，藉由下述第2供給步驟 而形成之保護被膜（硫酸鈉）之生成效率得到進一步提昇， 其結果使得可進一步防止Ag膠體發色，故而較好。 其中尤以含鹼金屬無機物質係含有Na及硼之無機物質更 好’其原因在於，利用本發明之製造方法所獲得之平面面 板用玻璃基板進而具有耐磨耗性。具體而言，含驗金屬無 機物質較好的是Na2B4〇7_10H2〇、Na2B4〇7，更好的是 Na2B4〇7**l〇H2〇 〇 藉由喷附含有Na及硼之無機物質，不僅供給Na亦供給 硼’其結果為，硼自底面擴散至上述玻璃基板之内部，使 上述玻璃基板本身之強度得到提昇。 因此’除了平面面板用玻璃基板以外’例如對DNa晶片 用玻璃基板、微晶片·生物晶片用玻璃基板等，亦可藉由 1646B9.doc •17-Zr02 : 0.2~6%, the total amount of soil oxide metal oxide components: 1 7~27%, the total amount of metal oxide components: 7~14%. In the present invention, from the viewpoint of strength and transmittance, the thickness of the glass substrate formed on the melt is preferably 1 to 3 mm. [Cold cooling step] The above-described cold cooling step is a step of quenching the glass substrate formed by the above-described forming step. Here, in the above-mentioned "the cold-cooling step", the step from the start of the sheet-shaped glass substrate being guided by the guide rolls 5 to the step of being conveyed to the quenching furnace 6 in a state of being continuous in the longitudinal direction is performed. . In the present invention, as the quenching furnace, the same quenching furnace as that of the (f)itf floating method can be used, and a heater or the like can be provided for controlling the temperature. Further, the cold cooling condition of the above-mentioned cold cooling furnace is the same as that of the usual floating method, and can be set at 55 〇 to 75 〇t at the inlet of the cold furnace, and is 200 to 300. (The temperature up to the temperature, the temperature drop rate can be set to 9 〇.. soil 1 〇 ° C / m. [First supply step] In the first manufacturing method of the present invention, the W supply step is directed to the glass substrate The step of supplying an alkali metal to the bottom surface by spraying an alkali metal-containing inorganic substance on the bottom surface (hereinafter also referred to as "the second supply step (i))" in the first supply step (first manufacturing method) Provided is a method for producing a glass substrate for a flat panel display, which is capable of maintaining good scratch resistance and preventing color development of Ag colloid by using an alkali metal-containing inorganic substance to supply an alkali metal to the bottom surface of the glass substrate. It is considered that the s〇2 gas sprayed by the second supply step described below preferentially reacts with the alkali metal supplied to the bottom surface, thereby preventing the s〇2 gas 164689.doc -15·201245058 from flowing to the top of the glass substrate. Further, by supplying an alkali metal to the bottom surface of the glass substrate by using an alkali metal-containing inorganic substance, formation of a sulfate derived from an alkaline earth metal (for example, "sulphuric acid, etc." can be suppressed, and Further, since the protective film of the sulfate (for example, sodium sulfate) which is known from the metal is efficiently produced, the amount of the S〇2 gas used can be reduced. Further, the sulfate of an alkaline earth metal such as calcium sulfate or barium sulfate can be used. In the second manufacturing method of the present invention, the first supply step is to spray an alkali metal to the top surface of the glass substrate. In the first supply step (second manufacturing method) A method for producing a glass substrate for a flat panel display, which uses an alkali metal-containing inorganic substance to supply an alkali metal to the top surface of the glass substrate, thereby preventing color development of the Ag colloid. Here, the so-called alkali metal-containing inorganic substance is as described above. , means an inorganic substance containing an alkali metal, for example, an inorganic substance containing lithium (Li), sodium (Na), potassium (K), planer (Cs), etc., as the inorganic substance containing Na, specifically For example, NaOH, Na2S, NaCl, NaF, NaBr, Nal, soda ash, NaNH2, sodium thorium, NaBH4, NaCN, NaN03, Na2B407-10H2 strontium (sodium tetraborate decahydrate), Na2B4〇7, ( C2H5) 4BNa, etc., may be used alone or in combination of two or more. 164689.doc -16 201245058 Specific examples of the inorganic substance containing κ include KOH, KC1, KF, KBr, and KI. , KCN, k2C〇3, potassium gluconate, KHF2, KN〇3, K2B4〇7_4H2〇 (potassium tetraborate tetrahydrate), K2B4〇7, KBF4, etc. 'These can be used alone! It is also possible to use two or more types together. Specific examples of the inorganic substance containing Cs include CsOH, CsCl, CsF, CsBr, Csl, acetonyl pyruvate, HCOsCs, CsN〇3, etc., which can be used alone! It is also possible to use two or more types together. For the reason shown below, the alkali metal-containing inorganic substance is preferably an inorganic substance containing Na. That is, in the manufacturing method of the first aspect of the present invention, the production efficiency of the protective film (sodium sulfate) formed by the second supply step described below is further improved, and as a result, the Ag colloid color can be further prevented from being further deteriorated. . In particular, the inorganic material containing an alkali metal inorganic substance containing Na and boron is more preferable. The reason is that the glass substrate for a flat panel obtained by the production method of the present invention has further abrasion resistance. Specifically, the inorganic metal-containing substance is preferably Na2B4〇7_10H2〇, Na2B4〇7, and more preferably Na2B4〇7**l〇H2〇〇 is not only supplied by spraying an inorganic substance containing Na and boron. Na is also supplied with boron. As a result, boron diffuses from the bottom surface to the inside of the glass substrate, and the strength of the glass substrate itself is improved. Therefore, the glass substrate for a DNa wafer, a glass substrate for a microchip or a biochip, and the like can be used in addition to a glass substrate for a flat panel, and can also be used by 1646B9.doc • 17-

S 201245058 =之擴散’來滿足高程度之耐檫傷性。 述玻璃m㈣頻㈣切錢㈣錢物質向上 m或頂面噴附，而向該等面供給鹼金屬 者，關於該喷附之時間（時 下所示之態樣。 )及嘴附方法’可適當例示以 喷附上述含鹼金屬益機物 ⑷制、“、獨…機物質之時間，若於第！供給步驟 笛…人土 弟製造方法）中均早於下述 第广步驟’則並無特別限定，具體而言，可與上述成 驟與上述徐冷步驟之間，可二=，但於上述成形步 痕的產生，故而較好。 纟抑制玻璃基板底面之傷 此處，所謂「與成形步驟同時」係指上述成形步驟中形 成玻璃基板之後緊接著，係包含於上述成形步驟之階段， 例如’於形成爐中設置有熔融錫浴（fl〇at _，漂浮浴）及 爐整體之出口部分（shieldrare，未遮蔽處）之情形時，可於 未遮蔽處噴附。又’所謂「與徐冷步驟同時」係指亦可於 徐冷爐之入口附近或徐冷爐上游側喷附之情形。此外，所 謂「上述成形步驟與上述徐冷步驟之間」係指亦可於在形 成爐與徐冷爐之間搬送玻璃基板期間進行噴附的情形。/ 另一方面，喷附上述含鹼金屬無機物質之方法Θ，於第i 供給步驟（第1製造方法）及第1供給步驟（第2製造方法）中 μ❹: 屬無機物質而使其、气 化，使用喷嘴將該汽化物質喷附至上述玻璃基板之底面2 方法；以及藉由加熱器加熱、紅外線燈加熱雷射加熱等 164689.doc 201245058 而使含驗金屬無機物質加熱汽化之方法等。 又，汽化物質之冑附較好的A ’於玻璃基板t玻璃轉移 點土 100°C之範圍的溫度下實施。尤其好的是玻璃基板之玻 璃轉移點-30 C〜玻璃轉移點+1〇〇。〇之範圍。其原因在於， 若於該溫度範圍下實施噴附’則玻璃會於玻璃轉移點軟 化’故而於該區域内形成膜，藉此可更有效地防止傷痕產 生。 具體而言’於使汽化物質有效汽化，且向玻璃基板表面 喷附時基板溫度不會急遽下降之方面而言，較好的是，於 550〜750°C下實施。 此外’關於气化物質之噴附量，於第i供給步驟⑷製 造方法）及第1供給步驟（第2製造方法）中均係，較好的是 0.2〜1〇L/m'更好的是〇.2〜3 L/m2，尤其好的是…—2。 若本發明之第以造方法中之喷附量在該範圍Θ，則供給 至上述玻璃基板之底面之驗金屬的供給量將達到充分，從 而進-步提昇與下述第2供給步财所噴附之s〇2氣體發生 反應而形成之保護㈣的生成效率。χ，若於本發明之第 2製造方法中喷附量在該範圍内，則可有效進行硼酸向玻 璃基板之擴散，故而可有效提昇耐磨耗性。 於使用四顯納十水合物作為上述含驗金屬無機物質之 情形時’可列舉如下方料作為較佳實絲樣：於玻璃基 板之㈣爐及徐冷爐以外之爐（例如，實施例中所使用之 大型管上爐等）中，以85Gt左右之溫度使四魏納汽化 後，利用噴嘴將該汽化物質喷附至7〇〇U右之形成爐或 I64689.doc •19· S. 201245058 徐冷爐、或者於該等爐間搬送之玻璃基板的底面或頂面。 藉由利用上述方法噴附上述含鹼金屬無機物質，向上述 玻璃基板之底面或頂面供給驗金I玻璃基板之底面或頂 面之鹼金屬之存在可藉由x射線光電子能譜儀（xps: x_ray ph〇t〇e】ectron spe价osc〇py)或螢光χ射線分析玻璃基板之 底面來加以確認。 [第2供給步驟] 於本發明之第1製造方法中，上述第2供給步驟係於上述 第1供、’·。步驟之後，向供給有上述鹼金屬之上述玻璃基板 之底面喷附S〇2氣體，而於該底面形成保護被膜之步驟。 (以下，亦稱為「第2供給步驟（第1製造方法）」）。 該第2供給步驟（第1製造方法）於供給有上述鹼金屬之上 述玻璃基板之底面形成保護被膜之方面，與通常之浮式法 之先前眾所周知之步驟不同。 即上述第2供給步驟（第1製造方法）係如下步驟：藉由 向矛i用上述第1供給步郵而供給有驗金屬之上述玻璃基板 之底面喷附S〇2氣體，而使鹼金屬與S〇2氣體反應，而於上 述玻璃基板之底面形成包含硫酸鹼鹽（例如，硫酸鈉等）之 保遵被膜。 另一方面，於本發明之第2製造方法中，上述第2供給步 驟係於上述第1供給步驟之後，向上述玻璃基板之底面噴 附S〇2氣體而於該底面形成保護被膜之步驟（以下，亦稱為 「第2供給步驟（第2製造方法）」），係與通常之浮式法之先 前眾所周知之步驟相同的步驟。 164689.doc •20· 201245058 關於上述第2供給步驟之s〇2氣體之喷附時間（時序）及噴 附方法，於第2供給步驟（第丨製造方法）及第2供給步驟（第2 製造方法）中，均可適當例示以下所示之態樣。. 喷附s〇2氣體之時間若晚於上述第丨供給步驟，則無特別 限定’自防止搬送過程中玻隸板表面之傷痕的觀點來考 慮，較好的是於上述第i供給步驟之後緊接著，更好的是 於上述成形步驟與上述徐冷步驟之間。再者，同時喷附各 個氣體係與各個氣體反應，由於難以形成被膜，故而欠 另一方面，喷附so2氣體之方法可利用與通常之浮式法 之先前眾所周知之方法相同的方法來進行。具體而言，例 如，可利用於玻璃基板寬度方向，自設置於玻璃基板下方 之喷嘴喷附的方法（例如’專利文獻3之請求項12中所揭示 之方法等）而實施。 然而’於本發明之第1製造方法中，與亦可利用由驗土 金屬得'之硫酸鹽（例如，硫_等）作為平面面板用玻璃 基板之保濩被膜的先前例相比， 、 H曰了確保同等之保護效果， 並且減少S〇2氣體之喷附量。立 /、项因可涊為在於，如上所 述’藉由第2供給步驟而喑 .„ ^ 噴附之S〇2氧體與供給至底面之鹼 金屬優先反應，而抑制該g Q痛牌 2乳體與鹼土金屬（Ca、Sr等） 的反應。具體而言，於本 5T月之第1製造方法中，s〇2氣體 之喷附量可縮小為〇.〇5〜25L/m2 尤其為0·05〜0.3 L/m2。 又，S〇2氣體之喷附軔妬 θ 。 較好的疋，於玻璃基板之玻璃轉移 點± 100 c之範圍的溫度下竇你 貫& ’更好的是於550〜750〇c下 164689.doc •21· 201245058 實施。若於該溫度下實施喷附’則可進一步提昇保護被膜 之生成效率’其結果為，可進一步防止Ag膠體發色。 本發明之製造方法係具備上述成形步驟 '徐冷步驟、第 1供給步驟、以及第2供給步驟之平面面板顯示器用玻璃基 板之製造方法，亦可進而具備以下所示之洗淨步驟。 (洗淨步驟） 於本發明之製造方法中，為了進行氣泡、異物、傷痕等 缺陷檢查，以獲得較高透過性，亦可視需要而具備對藉由 上述第2供給步驟而形成之保護被膜進行洗淨、去除之洗 淨步驟。 該洗淨步驟係通常之浮式法之先前眾所周知之步驟，關 於時間（時序）及洗淨方法，可適當例示以下所示之態樣。 上述洗淨步驟之時間若晚於上述第2供給步驟，則無特 別限定，但由於保護被膜係針對滾筒搬送過程中所產生之 玻璃基板之表面（底面）的傷痕而設置者，故而較好的是， 於上述徐冷步驟之最終階段或上述徐冷步驟之後緊接著。 另一方面，關於上述洗淨步驟之洗淨方法，由於在本發 明中是形成包括由鹼金屬得來之硫酸鹽（例如，硫酸鈉等 水浴性鹽）之保護被膜，故而可利用容易的方法來去除， 例如，可藉由水洗處理而去除。再者，當未實施上述第i ,、”’σ v驟而喷附s〇2氣體之情形時，形成於玻璃基板底 面之保護被獏將變為由驗土金屬得來之硫酸鹽（例如，硫 酸鈣等難水溶性鹽），而難以容易地洗淨。 本蚤月之第3態樣之平面面板顯示器用玻璃基板之製造 164689.doc -22- 201245058 方法（以下’亦稱為「本發明之第3製造方法」）係利用浮式 法來製造平面面板顯示器用玻璃基板者； 其具備成形步驟，將溶融玻璃於溶融錫上成形為玻璃基 板；且 具備··第1供給步驟，於550〜75(TC下向上述玻璃基板之 與上述溶融錫接觸之側的表面喷附含有驗金屬之無機物 質；以及第2供給步驟，於上述第1供給步驟之後，於 550〜750 C下向上述玻璃基板之與上述溶融錫接觸之側的 表面喷附S 〇2氣體。 此處，本發明之第3製造方法之成形步驟與本發明之製 ie方法中所說明者相同，就第丨供給步驟及第2供給步驟而 言亦係，除將溫度規定為55〇〜75〇υ以外，均與本發明之 第1裝造方法所說明者相同。又，於本發明之第3製造方法 中可進而具備上述洗淨步驟。 又本發明之第4態樣之平面面板顯示器用玻璃基板的 製造方法（以下，亦稱為「本發明之第4製造方法」）係利用 浮式法來製造平面面板顯示器用玻璃基板者； 其具備成形步驟，將熔融玻璃於熔融錫上成形為玻璃基 板；且 具備：第1供給步驟，於550〜75(rc下向上述玻璃基板之 未與上述溶融錫接觸之側的表面噴附含有鹼金屬之無機物 質’以及第2供給步驟’於上述第1供給步驟之後，於 550〜75〇°c下向上述玻璃基板之與上述熔融錫接觸之側的 表面噴附S02氣體。 164689.doc •23- 201245058 此處，本發明之第4製造方法之成形步驟與本發明之製 造方法中所說明者相同，就第1供給步驟及第2供給步驟而 言亦係，除將溫度規定為550〜750°C以外，均與本發明之 第2製造方法所說明者相同。又，於本發明之第4製造方法 中，亦可進而具備上述洗淨步驟。 本發明於在自本發明之第1製造方法至第4製造方法中， 使用含有Na及硼之無機物質之情形時，亦提供一種利用該 專方法而獲得之平面面板顯示器用玻璃基板。 具體而言，藉由將含有Na及硼之無機物質於上述第㈠共 給步驟中喷附至玻璃基板之底面及/或頂面，其後視需要 而實施上述洗淨步驟，可提供平面面板顯示器用玻璃基 較好的是，本發明之平面面板顯示器用玻璃基板為 組成。S 201245058 = spread 'to meet a high degree of resistance to bruises. The glass m (four) frequency (four) cut money (four) money material sprayed upward m or top surface, and the alkali metal is supplied to the surface, about the time of the spraying (the current situation shown) and the mouth attachment method ' Properly exemplified by spraying the above-mentioned alkali-containing metal-producing material (4), "the time of the material, if it is in the first! supply step flute...the method of manufacturing the human body" is earlier than the following broad step ' It is not particularly limited, and specifically, it may be between the above-mentioned step and the above-mentioned cold-cooling step, but it is preferable to produce the above-mentioned forming step, and it is preferable to suppress the damage of the bottom surface of the glass substrate. Simultaneously with the forming step, the glass substrate is formed in the forming step, and is then included in the forming step, for example, a molten tin bath (float bath) and a furnace are provided in the forming furnace. In the case of the exit part (shieldrare, unshielded), it can be sprayed at the unshielded place. Further, the term "simultaneously with the cold step" means that it can be sprayed near the entrance of the Xu cold furnace or upstream of the Xu cold furnace. Further, the term "between the above-described forming step and the above-mentioned cold-cold step" means that the glass substrate can be sprayed while being transported between the forming furnace and the quenching furnace. On the other hand, the method of spraying the above-mentioned alkali metal-containing inorganic substance, in the i-th supply step (first manufacturing method) and the first supply step (second manufacturing method), is an inorganic substance and is made into a gas. And a method of spraying the vaporized substance onto the bottom surface 2 of the glass substrate by using a nozzle; and a method of heating and vaporizing the metal-containing inorganic substance by heating by a heater, heating by a laser lamp, or the like by 164689.doc 201245058. Further, a good A' of the vaporized material is carried out at a temperature in the range of 100 ° C of the glass substrate t glass transition point soil. Particularly preferred is the glass transition point of the glass substrate -30 C ~ glass transfer point +1 〇〇. The scope of 〇. The reason for this is that if the coating is carried out in this temperature range, the glass is softened at the glass transition point, so that a film is formed in this region, whereby the occurrence of scratches can be more effectively prevented. Specifically, it is preferably carried out at 550 to 750 ° C in terms of effectively vaporizing the vaporized material and spraying the surface of the glass substrate without drastically lowering the temperature of the substrate. Further, it is preferable that the amount of the vaporized substance to be sprayed is the same as that of the first supply step (4) and the first supply step (the second production method), and preferably 0.2 to 1 〇L/m'. It is 〇.2~3 L/m2, especially good...~2. When the amount of the spray in the first method of the present invention is within this range, the supply amount of the metal to be supplied to the bottom surface of the glass substrate will be sufficient, and the second supply step will be further improved. The production efficiency of the protection (4) formed by the reaction of the sprayed s〇2 gas. When the amount of the coating in the second production method of the present invention is within this range, the diffusion of boric acid into the glass substrate can be effectively performed, so that the abrasion resistance can be effectively improved. When four-sensitization decahydrate is used as the above-mentioned metal-containing inorganic substance, the following materials can be cited as preferred solid filaments: in the furnace of the glass substrate (four) furnace and the furnace other than the quench furnace (for example, used in the examples). In a large-scale tube furnace, etc., after four Weiners are vaporized at a temperature of about 85 Gt, the vaporized material is sprayed to a 7 〇〇U right forming furnace by a nozzle or I64689.doc • 19· S. 201245058 Xu cold furnace, Or the bottom surface or top surface of the glass substrate conveyed between the furnaces. By spraying the above-mentioned alkali metal-containing inorganic substance by the above method, the presence of an alkali metal supplied to the bottom surface or the top surface of the glass substrate of the glass substrate I can be obtained by x-ray photoelectron spectroscopy (xps) : x_ray ph〇t〇e] ectron spe price osc〇py) or fluorescent ray analysis of the bottom surface of the glass substrate to confirm. [Second supply step] In the first production method of the present invention, the second supply step is the first supply. After the step, the S〇2 gas is sprayed onto the bottom surface of the glass substrate to which the alkali metal is supplied, and a protective film is formed on the bottom surface. (hereinafter, also referred to as "second supply step (first manufacturing method)"). In the second supply step (first production method), a protective film is formed on the bottom surface of the glass substrate on which the alkali metal is supplied, which is different from the previously known steps of the usual floating method. In other words, the second supply step (first manufacturing method) is a step of: spraying the S〇2 gas on the bottom surface of the glass substrate to which the metal is inspected by using the first supply step to the spear i, thereby causing the alkali metal The gas is reacted with the S〇2 gas, and a protective film containing an alkali sulfate salt (for example, sodium sulfate or the like) is formed on the bottom surface of the glass substrate. On the other hand, in the second manufacturing method of the present invention, the second supply step is a step of spraying S〇2 gas onto the bottom surface of the glass substrate and forming a protective film on the bottom surface after the first supply step ( Hereinafter, the "second supply step (second manufacturing method)") is the same step as the previously known steps of the usual floating method. 164689.doc •20· 201245058 The spraying time (timing) and the spraying method of the s〇2 gas in the second supply step, the second supply step (the second manufacturing method) and the second supply step (the second manufacturing step) In the method), the following aspects can be appropriately exemplified. When the s〇2 gas is ejected later than the above-described second supply step, it is not particularly limited to the viewpoint of preventing the flaw on the surface of the glazing plate during the transfer, and it is preferable that after the ith supply step Next, it is more preferable between the above forming step and the above-described quenching step. Further, simultaneous spraying of each gas system with each gas makes it difficult to form a film, and on the other hand, the method of spraying the so2 gas can be carried out by the same method as the conventionally known method of the usual floating method. Specifically, for example, it can be carried out by a method of spraying a nozzle provided under the glass substrate in the width direction of the glass substrate (for example, the method disclosed in claim 12 of Patent Document 3). However, in the first production method of the present invention, compared with the previous example in which the sulfate (for example, sulfur or the like) obtained from the soil-measuring metal is used as the protective film for the glass substrate for a flat panel, It ensures the same protective effect and reduces the amount of S〇2 gas sprayed. The vertical /, the factor can be attributed to, as described above, 'by the second supply step „. „ ^ The sprayed S〇2 oxygen body preferentially reacts with the alkali metal supplied to the bottom surface, and suppresses the g Q pain card 2 The reaction between the milk and the alkaline earth metal (Ca, Sr, etc.) Specifically, in the first manufacturing method of this 5T month, the amount of s〇2 gas sprayed can be reduced to 〇.〇5~25L/m2. It is 0·05~0.3 L/m2. In addition, the spray of 〇2 gas is 轫妒θ. The better 疋, at the temperature of the glass transition point of the glass substrate ±100 c, the sinus you are & It is good to be 164689.doc at 21:50 〇c. • 21·201245058. If the spraying at this temperature is carried out, the efficiency of the formation of the protective film can be further improved. As a result, the color of the Ag colloid can be further prevented. The manufacturing method of the present invention includes the above-described molding step 'the cold cooling step, the first supply step, and the second supply step, and the method for producing the glass substrate for a flat panel display, and may further include the following washing step. Net step) In the manufacturing method of the present invention, in order to carry out bubbles, foreign matter, A defect inspection such as a mark to obtain a high permeability, and a cleaning step of washing and removing the protective film formed by the second supply step as needed. The cleaning step is a usual floating method. The previously known steps, the time (time series) and the washing method, can be suitably exemplified as follows. The time of the washing step is not particularly limited, but the protective film is not later than the second supply step. It is provided for the flaw on the surface (bottom surface) of the glass substrate generated during the drum conveyance process, and therefore it is preferable to follow the final stage of the above-mentioned cold cooling step or the above-described cold cooling step. In the cleaning method of the above-described washing step, since a protective film comprising a sulfate derived from an alkali metal (for example, a water-bathable salt such as sodium sulfate) is formed in the present invention, it can be removed by an easy method, for example, It can be removed by a water washing treatment. Further, when the above-mentioned i, "" σ v is suddenly applied and the s〇 2 gas is sprayed, it is formed on the bottom of the glass substrate. The protective layer of the surface will become a sulfate derived from the soil (for example, a hardly water-soluble salt such as calcium sulfate), and it is difficult to wash it easily. Manufacture of a glass substrate for a flat panel display of the third aspect of the month 164689.doc -22- 201245058 The method (hereinafter also referred to as "the third manufacturing method of the present invention") is to manufacture a flat panel by a floating method. a glass substrate for a display; comprising: a molding step of forming a molten glass on a molten tin into a glass substrate; and providing a first supply step of contacting the molten tin to the glass substrate at 550 to 75 (TC) The surface of the side is sprayed with the inorganic substance containing the metal; and the second supply step, after the first supply step, the surface of the glass substrate on the side in contact with the molten tin is sprayed at 550 to 750 C. 2 gas. Here, the forming step of the third manufacturing method of the present invention is the same as that described in the method of the present invention, and the second feeding step and the second supplying step are also performed except that the temperature is specified as 55. Other than 〇υ75〇υ, it is the same as that described in the first method of the present invention. Further, in the third manufacturing method of the present invention, the cleaning step may be further provided. Further, the fourth aspect of the present invention flat A method for producing a glass substrate for a panel display (hereinafter also referred to as "the fourth manufacturing method of the present invention") is a method for producing a glass substrate for a flat panel display by a floating method; and a molding step for forming molten glass in molten tin The upper surface is formed into a glass substrate; and the first supply step is performed, and 550 to 75 (the inorganic material containing an alkali metal is sprayed onto the surface of the glass substrate that is not in contact with the molten tin on the surface of the glass substrate) and the second supply step After the first supply step, the SO 2 gas is sprayed onto the surface of the glass substrate on the side in contact with the molten tin at 550 to 75 ° C. 164689.doc • 23- 201245058 Here, the present invention (4) The molding step of the manufacturing method is the same as that described in the production method of the present invention, and the first supply step and the second supply step are also the same as the present invention except that the temperature is set to 550 to 750 °C. In the fourth manufacturing method of the present invention, the cleaning step may be further provided. The present invention is also applicable to the first manufacturing method to the fourth manufacturing method of the present invention. In the method, when an inorganic substance containing Na and boron is used, a glass substrate for a flat panel display obtained by the special method is also provided. Specifically, an inorganic substance containing Na and boron is used in the above (1) The common step is sprayed onto the bottom surface and/or the top surface of the glass substrate, and the cleaning step is performed as needed, and the glass substrate for the flat panel display can be provided. Preferably, the glass substrate for the flat panel display of the present invention is provided. For the composition.

Si02 : 45-70%， Al2〇3 : 0〜20%， Ca〇 : 〇〜2〇%， Zr02 : 〇~13〇/〇 , ’上述玻璃 驗土金屬氧化物成分之合計量： 驗金屬氧化物成分之合計量： 40% .Si02 : 45-70%, Al2〇3 : 0~20%, Ca〇: 〇~2〇%, Zr02 : 〇~13〇/〇, 'The total amount of the above-mentioned glass soil metal oxide components: metal oxidation Total composition of ingredients: 40%.

硼濃度為2〜6原子％，較好的是2 面較好的是，頂面之平均 〖〜4原子。/。，且硼向上述玻 164689.doc '24- 201245058 璃基板之内部之擴散深度為20〜80 nm，較好的是3〇〜5〇 nm 〇 又，作為其他具體組成，可列舉與上述組成相同者，作 為成形於溶融錫上之玻璃基板的組成。 _於本發明中，上述玻璃基板之上述底面或頂面之平均侧 濃度可作為利用X射線光電子能譜法而任意測定5點時之平 均值而求得。 再者，於X射線光電子能譜法中，使用XPS能譜儀（55〇〇 型，細公司製造）’將藉由單色器而單色化之x射線A1Ka 線作為X射線源q，\射線光電子之檢測角為75。，為了 進行帶電修正’照射級聯射叢（cascade sh〇wer)來實施測 定。 於本發明中，硼向玻璃基板内部之擴散深度可藉由 二次離子 SIMS)，自 始評估。 開 質譜法（secondary ion mass spectr〇sc〇py 到達與基底同等程度之二次離子強度之深度 ”體而5 ’利用二次離子質譜儀（AE)EpT1〇1〇，Ulvac △司製造）於玻璃基板上之5點分別測定5點之擴散深 度，求出其平均值。 此處，將濺散時間換算成濺散深度係利用si〇2換算（4 nm 1 mln)而進行的。再者，於一次離子為氧離子束，加 、、電堅為5 keV ’束電流為4〇〇 nA，—次離子之入射角度 才對於试料面之法線45度，束掃描範圍為4〇〇χ4〇() 之條件下進行測定β 164689.doc -25· 201245058 於本發明之平面面板用玻璃基板中，上述玻璃基板之上 述底面或頂面之平均硼濃度為2〜6原子％，較好的是2〜4原 子％’且硼向上述玻璃基板之内部之擴散深度為2〇〜8〇 nm，較好的是3〇〜5〇 nm，故而玻璃基板本身之強度得到 提昇，抗磨耗性優異，於去除保護被膜後之搬送或加工步 驟中耐傷性亦優異。藉由使硼自底面或頂面擴散至玻璃基 板之内部而殘留於玻璃基板之表層，可提昇耐磨耗性及耐 傷性’其理由可認為在於玻璃之網狀構造變得牢固。 本發明之平面面板顯示器用玻璃基板在實施上述洗淨步 驟之剛自不待言，在視需要而實施上述洗淨步驟之後，侧 亦殘留於玻璃基板之表層，故而可持續抑制玻璃基板背面 之傷痕的產生，故而較好。 再者，可推測’於本發明之平面面板顯示器用玻璃基板 中硼會殘留於玻璃基板之表層之理由在於，藉由上述第！ 供給步驟’棚易於進入玻璃基板内部，且易於殘留於玻璃 基板表層。 又，本發明之平面面板顯示器用玻璃基板中，自上述玻 璃基板之頂面至0.1 μιη之深度為止的平均Η原子濃度較好 的是2.5莫耳％以下’更好的是2.0莫耳％以下。若平均η原 子濃度在該範圍内’則引起上述Ag+與Η+之交換反應的機 會將減少’於銀電極形成時，Ag+不會進入至表面層，從 而可進而防止Ag膠體發色。 此處，自上述玻璃基板之頂面至0.1 μιη之深度為止的平 均Η原子濃度可使用二次離子質譜儀（ADEPT1010，Ulvac 164689.doc _ 26 · 201245058 △司製造）’測定自頂面至0. i μπι之深度為止之間的5 作為其平均值而求出。再者，於一次離子為Cs+，加 速電壓為5 kev，束電流為4GG nA，—次離子之入射角度 為相對於^式料面之法線6〇度，束掃描範圍為⑽ 之條件下進行測定。 因此，本發明亦可提供一種平面面板顯示器用玻璃基 板，其以氧化物為基準且以質量百分率表示，含有：The boron concentration is 2 to 6 atom%, preferably 2 sides, and the average of the top surface is 〜4 atoms. /. And the diffusion depth of boron to the inside of the glass substrate 164689.doc '24- 201245058 is 20 to 80 nm, preferably 3 〇 to 5 〇 nm 〇 again, as other specific compositions, the same as the above composition As a composition of a glass substrate formed on molten tin. In the present invention, the average side concentration of the bottom surface or the top surface of the glass substrate can be obtained by arbitrarily measuring the average value at five points by X-ray photoelectron spectroscopy. Further, in the X-ray photoelectron spectroscopy method, an x-ray A1 Ka line monochromatized by a monochromator is used as an X-ray source q, using an XPS spectrometer (Model 55 ,, manufactured by Fine Co., Ltd.). The detection angle of the ray photoelectron is 75. The measurement is carried out in order to perform a charge correction 'cascade sh〇wer'. In the present invention, the diffusion depth of boron into the interior of the glass substrate can be evaluated initially by secondary ion SIMS). Open mass spectrometry (secondary ion mass spectr〇sc〇py reaches the depth of secondary ion intensity equivalent to the substrate) and 5 'Using secondary ion mass spectrometer (AE) EpT1〇1〇, manufactured by Ulvac △) The diffusion depth of 5 points was measured at 5 points on the substrate, and the average value was obtained. Here, the spattering time was converted into a spatter depth by si〇2 conversion (4 nm 1 mln). The primary ion is an oxygen ion beam, and the electric current is 5 keV. The beam current is 4〇〇nA. The incident angle of the secondary ion is 45 degrees to the normal of the sample surface, and the beam scanning range is 4〇〇χ4. In the glass substrate for a flat panel of the present invention, the average boron concentration of the bottom surface or the top surface of the glass substrate is preferably 2 to 6 atom%, preferably 164. 689.doc -25. It is 2 to 4 atom%' and the diffusion depth of boron to the inside of the glass substrate is 2 〇 to 8 〇 nm, preferably 3 〇 to 5 〇 nm, so that the strength of the glass substrate itself is improved, and the abrasion resistance is excellent. Resistant to the transfer or processing steps after removal of the protective film It is excellent in properties. By allowing boron to diffuse from the bottom surface or the top surface to the inside of the glass substrate and remaining on the surface layer of the glass substrate, the abrasion resistance and the scratch resistance can be improved. The reason is that the mesh structure of the glass becomes firm. The glass substrate for a flat panel display of the present invention is self-evident after performing the above-described cleaning step, and the side remains on the surface of the glass substrate after performing the above-described cleaning step as needed, so that the back surface of the glass substrate can be continuously suppressed. Further, it is preferable that the reason why the boron remains on the surface layer of the glass substrate in the glass substrate for a flat panel display of the present invention is that the shed is easily accessible to the glass substrate by the above-mentioned first supply step Further, in the glass substrate for a flat panel display of the present invention, the average germanium atom concentration from the top surface of the glass substrate to a depth of 0.1 μm is preferably 2.5 mol% or less. 'Better than 2.0 mol%. If the average η atom concentration is within this range', the above exchange of Ag+ and Η+ is caused. The opportunity should be reduced. When the silver electrode is formed, Ag+ does not enter the surface layer, thereby preventing the Ag colloid from developing. Here, the average germanium atom concentration from the top surface of the glass substrate to a depth of 0.1 μm It can be determined by using a secondary ion mass spectrometer (ADEPT1010, manufactured by Ulvac 164689.doc _ 26 · 201245058 △) to measure 5 from the top surface to the depth of 0.1 μ μm as the average value. The primary ion is Cs+, the accelerating voltage is 5 kev, and the beam current is 4GG nA. The incident angle of the secondary ion is 6 degrees to the normal of the ^-type surface, and the beam scanning range is (10). Accordingly, the present invention can also provide a glass substrate for a flat panel display, which is expressed in terms of mass percentage based on oxides and contains:

Si〇2 : 45〜70%，Si〇2: 45~70%,

Al2〇3 : 0〜20%，Al2〇3 : 0~20%,

CaO : 〇〜2〇% ,CaO : 〇~2〇%,

Zr02 : 〇〜13〇/0， 驗土金屬氧化物成分之合計量：5〜40〇/〇， 驗金屬氧化物成分之合計量：5〜3 0%， 至少其中一表面之平均硼濃度為2〜6原子％，且硼自該 表面向内部之擴散深度為2〇〜80 nm。 [實施例] 以下’利用實施例來對本發明進行具體說明，但本發明 並未限定於此。 (實施例1) 使用圖2所示之實驗裝置。圖2係實施例中所使用之大型 管狀爐之剖面圖。 具體而言，於可調節溫度之大型管狀爐丨丨中設置石英管 12，於石英管12中放置厚度為2.8 mm之平面面板顯示器用 玻璃基板13(10 cm見方）’將大型管狀爐11加熱至6〇〇°C。 164689.doc -27·Zr02 : 〇~13〇/0, the total amount of soil oxide metal oxide components: 5~40〇/〇, the total amount of metal oxide components: 5~3 0%, the average boron concentration of at least one surface is 2 to 6 atom%, and the diffusion depth of boron from the surface to the inside is 2 〇 to 80 nm. [Examples] Hereinafter, the present invention will be specifically described by way of Examples, but the present invention is not limited thereto. (Example 1) The experimental apparatus shown in Fig. 2 was used. Figure 2 is a cross-sectional view of a large tubular furnace used in the examples. Specifically, a quartz tube 12 is disposed in a large tubular furnace of adjustable temperature, and a glass substrate 13 (10 cm square) for a flat panel display having a thickness of 2.8 mm is placed in the quartz tube 12 to heat the large tubular furnace 11. Up to 6 ° ° C. 164689.doc -27·

S 201245058 此處，作為「平面面㈣示㈣破㈣板」，係使用以氧 化物為基準且以質量百分率表示，具有如下組成之玻璃：S 201245058 Here, as the "planar surface (four) display (four) broken (four) plate", a glass having the following composition based on an oxide and expressed in mass percentage is used:

4.8、SrO4.8, SrO

Si〇2 ： 58.6 > A1203 : 6.9 . Mg〇 : 1.9. CaO：Si〇2 : 58.6 > A1203 : 6.9 . Mg〇 : 1.9. CaO:

Zr . 〇 6 9、Ba〇 · 7 9、Na2〇 : 4·〇 m.l、Zr〇2 :Zr . 〇 6 9 , Ba 〇 · 7 9 , Na 2 〇 : 4 · 〇 m.l, Zr 〇 2 :

Fe203 . G.G9。再者，上述玻璃之玻璃轉移點為繼。c。 人，將放入至氧化鋁晶舟丨4中之四硼酸鈉十水合物之 試齊U5局。p力^熱至大約85〇 c而使其汽化將該汽化物質 自石英管之端向箭頭16所示方向噴附，藉此將四硼酸鈉供 至平面面板用玻璃基板13之表面（底面）。此時之四硼酸 鈉十水合物之喷附量為〇.4 L/m2,平面面板用玻璃基板13 之溫度為600°C。 其次，以使對供給有鈉之平面面板顯示器用玻璃基板13 之表面（底面）的喷附量為0」L/m2之方式，自箭頭17所示 方向嘴附S〇2氣體，形成保護被膜，而製造附有保護被 膜之平面面板顯示器用玻璃基板。此時之平面面板顯示器 用玻璃基板13之溫度為600°C。 再者，本實施例之條件與在上述成形步驟與上述徐冷步 驟之間喷附含鹼金屬無機物質之後，緊接著喷附s〇2氣體 之條件相同。 (實施例2) 除了將S〇2氣體之噴附量設為〇.4 L/m2以外，以與實施例 1相同之方法製造附有保護被膜之平面面板顯示器用玻璃 基板。 (實施例3) 164689.doc -28- 201245058 除了將so2氣體之喷附量設為1〇1^2以外，以與實施例 1相同之方法製造附有保護被膜之平面面板顯示器用玻璃 基板。 (比較例1) 除了未使用四硼酸鈉，而僅噴附S02氣體以外，以與實 施例1相同之方法製造时保護被膜之平面面板顯示器: 玻璃基板。 (比較例2) 除了未使用四硼酸鈉，而僅喷附s〇2氣體以外，以與實 施例2相同之方法製造附有保護被膜之平面面㈣示器用 玻璃基板。 (比較例3) 除了未使用四硼酸鈉，而僅喷附s〇2氣體以外，以與實 施例3相同之方法製造附有保護被膜之平面面板顯示器用 玻璃基板。 (比較例4) 除了未使用四硼酸鈉，亦未喷附s〇2氣體，而僅於7〇〇。〇 下加熱I5分鐘以外，以與實施例丨相同之方法製造平面面 板顯示器用玻璃基板。 (比較例5) 除了未使用四硼酸鈉’且亦未喷附s〇2氣體以外，以與 實施例1相同之方法製造平面面板顯示器用玻璃基板。 利用以下所示之方法，對實施例^及比較例1〜3中所獲 考于之各附有保護被膜之平面面板顯示器用玻璃基板的保護 164689.doc -29· 201245058 被膜之附著量、耐傷性、平均硼濃度.擴散深度、頂面之 平均Η原子濃度、頂面之黃度指數及对磨耗性進行測定及 評價。將該結果揭示於下述表1中。 再者’關於比較例4及5中所獲得之各平面面板顯示器用 玻璃基板，由於未喷附S〇2氣體，而未形成有保護被膜， 故而利用以下所示之方法僅對财磨耗性進行測定。將該結 果不揭於下述表1中。 &lt;保護被膜附著量&gt; 將所獲彳于之各附有保護被膜之平面面板用玻璃基板之保 護被膜溶解於純水中’使用ICP發光分析法來對硫進行定 2： ’並使用原子吸光法來對鈉、巧及鎮進行定量。 根據該等定量值，算出附著於底面之硫酸鹽量作為保護 被膜之附著量。再者，該附著量係作為自所獲得之1〇片附 有保護被膜之平面面板顯示器用玻璃基板所算出的平均值 而求得。 &lt;耐傷性&gt; 耐傷性之評價係利用依據JIS R322丨（！ 99〇年）之Taber測 試而進行的。再者，Taber測試係於使用Taber測試機 (Tdedyne Taber Model503)，磨耗輪固定為 cs_1〇F，載荷 為250g，磨耗次數固定為3次之條件下實施的。 其後，為了去除用作測試體之各附有保護被膜之平面面 板顯示器用玻璃基板的保護被膜，於2〇〇Ci純水之流水下 (3升/分鐘）以淋浴之方式水洗基板3〇秒鐘。 用顯微鏡來觀察去除保護被膜而獲得之玻璃基板之表 164689.doc •30· 201245058 面’測定處於1 cmxi cm見方内之長軸方向長度為〇2麵 以上傷痕的數量（傷痕產生個數）。測定部設為供丁加測試 之部位的中央部(參照圖3)。於圖3中，於測試體(平面面板 顯示器用玻璃基板）18中利用磨耗輪而形成磨耗部19，測 定部20成為磨耗部19之中央部。 再者，傷痕產生個數之測定係對各玻璃基板之每一片上 之任意10點而實施’並求出其平均值。進而，傷痕產生個 數係作為自所獲得之10片玻璃基板算出的平均值而求得。 &lt;平均硼濃度.擴散深度&gt; (1)於2(TC純水（流速：3升/分鐘）所流注之處，對所獲得 之各附有保護被膜之平面面板顯示.器用玻璃基板進行水 洗，去除保護臈。其後，作為利用χ射線光電子能譜法而 對5點進行測定後之平均值’而求出洗淨後玻璃基板底面 之平均硼濃度。再者，於χ射線光電子能譜法中，使用 XPS能譜儀（5500型，ΡΗΙ公司製造），將藉由單色器而單色化 之X射線ΑΙΚα射線作為X射線源。又，χ射線光電子之檢測角 為75°，為了進行帶電修正，照射級聯射叢來實施測定。 下述表1中，比較例丨〜3之平均硼濃度一欄為「」，此表 示無法檢測出蝴。 (2)硼向玻璃基板内部之擴散深度係藉由利用二次離子 質譜法(SIMS)’自達到與基底同等程度之二次離子強度之 深度開始評估。 具體而S ’利用二次離子質譜儀（ADEPT1010，Ulvac hi a司製k )，於洗淨後之玻璃基板上之5點上分別測定$ S. 164689.doc •31· 201245058 點之擴散深度，求出其平均值。此處，將濺散時間換算成 激散深度係藉由Si〇2換算（4 nm=l min)而進行的。 再者，於一次離子為氧離子束，加速電壓為5 keV，束電 流為400 nA，一次離子之入射角度為相對於試料面之法線“ 度’束掃描範圍為400x400 μιη2之下條件下進行測定。 下述表1中，比較例1〜3之擴散深度一攔為「_」，此表示 擴散無法確認。 &lt;頂面之平均Η原子濃度&gt; 使用二次離子質譜儀（ADEPT101〇，uivac Phi公司製 造）’測定自頂面至0·1 μιη之深度為止之間的5點，作為其 平均值而求出所獲得之各附有保護被膜之平面面板顯示器 用玻璃基板之自玻璃基板頂面至〇1 μηι之深度為止的平均 Η原子濃度。再者，於一次離子為Cs+，加速電壓為5 keV ’束電流為4〇〇 nA，一次離子之入射角度為相對於試 料面之法線60度’束掃描範圍為200x200 μπι2之條件下進 行測定。 &lt;頂面之黃度指數（b*)&gt; 所獲彳于之各附有保護被膜之平面面板顯示器用玻璃基板 之玻璃基板頂面的黃度指數，係利用日立製作所製造之自 動記錄分光光度計（U-3500型），依據JIS-Z8729而測定樣品 (於頂面塗佈厚度為20 μηι之Ag，於110。(：下進行乾燥處理 20分鐘後，於560eC下進行燒成處理60分鐘’冷卻後利用 确酸而去除Ag者）。再者，50〜350 t：之熱膨脹係數係於 83xl〇'7/°c、軟化點為570°C之條件下測定。 164689.doc •32· 201245058 〈耐磨耗性&gt; 耐磨耗性係藉由調杳Taber測·^ &amp; μ r/：Bj或前後濁度率之變化率（濁 度變化率）而進行的。 首先，用濁度計測定所獲得之各平面面板用玻璃基板之 濁度率。Fe203. G.G9. Furthermore, the glass transition point of the above glass is continued. c. The person will be placed in the U5 tube of sodium tetraborate decahydrate in the alumina boat. The p-force is heated to about 85 〇c to vaporize the vaporized material from the end of the quartz tube in the direction indicated by the arrow 16, whereby the sodium tetraborate is supplied to the surface (bottom surface) of the glass substrate 13 for the flat panel. . At this time, the amount of sodium tetraborate decahydrate sprayed was 〇.4 L/m2, and the temperature of the glass substrate 13 for flat panel was 600 °C. Then, the amount of the film to be applied to the surface (bottom surface) of the glass substrate 13 for the flat panel display having sodium is 0"L/m2, and the gas is attached to the nozzle from the direction indicated by the arrow 17 to form a protective film. A glass substrate for a flat panel display with a protective film is produced. The temperature of the glass substrate 13 for the flat panel display at this time was 600 °C. Further, the conditions of the present embodiment are the same as the conditions for spraying the s〇2 gas immediately after the alkali metal-containing inorganic substance is sprayed between the above-described forming step and the above-mentioned cold step. (Example 2) A glass substrate for a flat panel display with a protective film was produced in the same manner as in Example 1 except that the amount of the S〇2 gas sprayed was changed to 〇4 L/m2. (Example 3) 164689.doc -28-201245058 A glass substrate for a flat panel display with a protective film was produced in the same manner as in Example 1 except that the amount of the so2 gas to be sprayed was changed to 1 〇 1 2 . (Comparative Example 1) A flat panel display for protecting a film at the time of production in the same manner as in Example 1 except that sodium tetraborate was not used and only the SO 2 gas was sprayed: a glass substrate. (Comparative Example 2) A flat surface (four) glass substrate with a protective film was produced in the same manner as in Example 2 except that sodium sulfoxide was not used and only s〇2 gas was sprayed. (Comparative Example 3) A glass substrate for a flat panel display with a protective film was produced in the same manner as in Example 3 except that sodium sulfoxide was not used and only s〇2 gas was sprayed. (Comparative Example 4) The s〇2 gas was not sprayed except for the use of sodium tetraborate, but only 7 〇〇. A glass substrate for a flat panel display was produced in the same manner as in Example 以外 except that the crucible was heated for 5 minutes. (Comparative Example 5) A glass substrate for a flat panel display was produced in the same manner as in Example 1 except that sodium tetraborate was not used and s〇2 gas was not sprayed. The adhesion of the glass substrate for the flat panel display with the protective film obtained in each of the examples and the comparative examples 1 to 3 was 164689.doc -29·201245058 by the method shown below. The average boron concentration, the diffusion depth, the average erbium atom concentration of the top surface, the yellowness index of the top surface, and the wearability were measured and evaluated. The results are disclosed in Table 1 below. In addition, the glass substrates for the flat panel display obtained in Comparative Examples 4 and 5 were not sprayed with the S〇2 gas, and the protective film was not formed. Therefore, only the fiscal wearability was performed by the method described below. Determination. This result is not disclosed in Table 1 below. &lt;Protection of the amount of the coating film to be adhered&gt; The protective film of the glass substrate for a flat panel to which the protective film is attached is dissolved in pure water. 'The sulfur is determined by ICP emission spectrometry 2' and the atom is used. Absorbance is used to quantify sodium, Qiao and Zhen. Based on these quantitative values, the amount of sulfate adhering to the bottom surface was calculated as the amount of adhesion of the protective film. In addition, the amount of adhesion was determined as an average value calculated from a glass substrate for a flat panel display having a protective film obtained from a single film. &lt;Surability/resistance&gt; The evaluation of the scratch resistance was carried out using a Taber test in accordance with JIS R322 (! 99 years). Further, the Taber test was carried out using a Taber tester (Tdedyne Taber Model 503) with a wear wheel fixed at cs_1〇F, a load of 250 g, and a fixed number of wear times of three times. Thereafter, in order to remove the protective film used as the glass substrate for the flat panel display with the protective film as the test body, the substrate was washed by shower under a stream of 2 〇〇Ci pure water (3 liters/min). Seconds. The surface of the glass substrate obtained by removing the protective film by a microscope was observed. 164689.doc • 30· 201245058 The surface was measured in the length of 1 cm x cm square in the direction of the long axis, and the number of scratches on the surface of the 〇2 surface (the number of scratches). The measurement unit is a central portion of a portion for which the test is performed (see Fig. 3). In Fig. 3, a wear portion 19 is formed by a wear wheel in a test body (glass substrate for a flat panel display) 18, and the measurement portion 20 serves as a central portion of the wear portion 19. Further, the measurement of the number of scars was carried out for any 10 points on each of the glass substrates, and the average value thereof was determined. Further, the number of occurrences of the flaws was determined as an average value calculated from the obtained ten glass substrates. &lt;Average Boron Concentration. Diffusion Depth&gt; (1) At the place where 2 (TC pure water (flow rate: 3 liters/min) is injected, the obtained flat panel display with protective film is used. The water was washed to remove the protective ruthenium. Then, the average boron concentration of the bottom surface of the glass substrate after washing was determined as the average value of five points measured by X-ray photoelectron spectroscopy. In the energy spectrum method, an XPS spectrometer (Model 5500, manufactured by Nippon Steel Co., Ltd.) was used, and X-ray ΑΙΚα rays monochromated by a monochromator were used as an X-ray source. Further, the detection angle of X-ray photoelectrons was 75°. In order to perform the charge correction, the cascading ray is irradiated to perform the measurement. In the following Table 1, the average boron concentration column of the comparative example 丨3 is "", which means that the butterfly cannot be detected. (2) Boron to the glass substrate The internal diffusion depth is evaluated by using secondary ion mass spectrometry (SIMS) to achieve the same depth as the secondary ionic strength of the substrate. Specifically, S' uses a secondary ion mass spectrometer (ADEPT1010, Ulvac hi a division) System k), after washing the glass At 5 o'clock on the substrate, measure the diffusion depth of $ S. 164689.doc •31· 201245058 points and find the average value. Here, the spattering time is converted into the exudation depth by Si〇2 conversion (4 Furthermore, in the case where the primary ion is an oxygen ion beam, the accelerating voltage is 5 keV, the beam current is 400 nA, and the incident angle of the primary ion is a normal "degree" beam scan with respect to the sample surface. The measurement was carried out under the conditions of 400×400 μm 2 . In Table 1 below, the diffusion depths of Comparative Examples 1 to 3 were “_”, which means that the diffusion could not be confirmed. &lt;The average Η atomic concentration of the top surface&gt; The secondary ion mass spectrometer (ADEPT101®, manufactured by uivac Phi Co., Ltd.) measured five points from the top surface to a depth of 0.1 μm, and obtained the average of the obtained protective film planes as the average value. The average germanium atomic concentration of the glass substrate from the top surface of the glass substrate to the depth of 〇1 μηι is used for the panel display. Furthermore, the primary ion is Cs+, the accelerating voltage is 5 keV, and the beam current is 4〇〇nA. Incident angle is relative to the sample The normal line is measured under the condition that the beam scanning range is 200×200 μπι 2 . &lt;The yellowness index of the top surface (b*)&gt; The glass substrate for the flat panel display each having the protective film is obtained. The yellowness index of the top surface of the glass substrate was measured by an automatic recording spectrophotometer (U-3500 type) manufactured by Hitachi, Ltd., and the sample was measured in accordance with JIS-Z8729 (Ag coated at a top surface of 20 μηι, at 110). (: After drying for 20 minutes, the baking treatment was carried out at 560 ° C for 60 minutes. After cooling, the Ag was removed by acid.) Further, the coefficient of thermal expansion of 50 to 350 t: was measured at 83 x 1 〇 '7 / ° C and the softening point was 570 ° C. 164689.doc •32· 201245058 <Abrasion resistance> The abrasion resistance is measured by the Taber measurement ·^ &amp; μ r/:Bj or the change rate of the turbidity rate before and after (turbidity change rate) of. First, the haze ratio of each of the obtained glass substrates for a flat panel was measured with a turbidimeter.

繼而’對各平面面板用玻璃基板，進行依據JIS R3221(1990年）之Taber測試。再者，丁化^測試係於使用 Taber測試機（Tdedyne Taber M〇del5〇3)，磨耗輪固定為 cs· l〇F ’载荷固定為500 g之條件下進行的。 鉍而，藉由濁度計而測定1〇〇〇次Taber磨耗後之濁度 率’根據Taber測試前之濁度率，求出其變化率。 此處，濁度值可利用散射光（Td)及透射光（Tt)而定義為 下式。 濁度率=(Td/Tt)xl00°/〇 又，濁度率（Η)之變化率（ΔΗ)可用下式表示。 ΑΗ=磨耗次數1000次後之濁度率H-Taber測試前之濁度率Η [表1] 四硼酸鈉 喷附量 (L/m2) 302氣體 喷附量 (L/m2) 保護被膜 附著量 (mg/10 cm 見方） 耐傷性 產生個 數(個 /10 cm 見方） 平均硼 濃度 (at%) 擴散 深度 (nm) Η原子 濃度 (mol%) 黃度 指數 耐磨耗 性濁度 變化率 (%) 實施例1 0.4 0.1 0.13 25 3.5 40 1.0 3.4 2.5 實施例2 0.4 0.4 0.51 3 3.5 40 1.2 3.5 2.5 實施例3 0.4 1.0 1.35 0 3,5 40 1,8 4.3 2.5 比較例1 - 0.1 0.1 48 - - 1.6 4.1 4.5 比較例2 - 0.4 0.1 30 - - 2.5 5.5 4.5 比較例3 - 1.0 0.5 6 - - 4.3 7.6 4.5 比較例4 - • * - - - - - 4.5 比較例5 - - - - - 4.5 -33· 164689.doc 201245058 由表1所示之結果可知，使用四蝴酸納所獲得之實施例 1〜3之平面面板顯示器用玻璃基板與比較例卜3相比，即使 s〇2氣體噴附量為同等以下，亦可_傷性良好地保持在 同等以上，從而可抑制頂面之黃度指數，即Ag膠體發色。 又，即使附著等量之硫酸納，㉛，比較實施例i與比較 例2亦可知，使用四侧酸鈉而獲得之實施例ι之平面面板顯 示器用玻璃基板的傷痕產生個數較少。其原因在於，藉由 賴散至玻璃基板，玻璃基板本身之抗磨擦性得到提昇。 又，已確認，實施例卜3之平面面板用玻璃基板經通常 之水洗後，形成於玻璃基板表面之保護被膜得到去除，而 呈現出潔淨之表面。與之相對，對於比較例丨〜3之平面面 板用玻璃基板，即使進行通常之水洗，形成於玻璃基板表 面之保護被膜亦無法去除而殘留下來。又，若測定所殘留 下來之膜成分，則為硫酸鈣及硫酸鏍。 此外，已知悉’實施例卜3之平面面板用玻璃基板由於 侧擴散’故而較之比較例卜5之平面面板用玻璃基板，濁 度變化率減小，耐磨耗性亦得到提昇。 參照詳細或特定之實施態樣對本發明進行了說明，但對 業者而言，當知在不脫離本發明之精神及範圍下可加以各 種變更或修正。 本申請案係根據2006年7月7日申請之日本專利申請案 (日本專利特願2006_188036)者’其内容作為參照而引用於 此。 [產業上之可利用性] 164689.doc •34· 201245058 根據本發明’可提供-種可維持良好之耐傷性，並且防 止Ag膠體發色之平面面板顯示μ麵基板之製造方法、 以及利用該製造方法而獲得之平面面板顯示器用玻璃基 板。 又，本發明不僅適用於PDP，而且在FED、sed等之 中’亦可維持良好之耐傷性，並騎止倾體發色，故而 亦適用於FED、SED等。 【圖式簡單說明】 圖1係表示利用浮式法之玻璃製造線之一例的概念圖。 圖2係實施例中所使用之大型管狀爐之剖面圖。 圖3係表示耐傷性評價中所使用之Taber實驗機之磨耗輪 所觸抵之部分（磨耗部）、傷痕數測定部位（測定部）的說明 圖〇 【主要元件符號說明】 1 溶融錫 2 溶融錫浴 3 溶融窯 4 溶融玻璃 5 引導輥 6 徐冷爐 11 大型管狀爐 12 石英管 13 平面面板顯示器用玻璃基板 14 氧化鋁晶舟Then, the Taber test according to JIS R3221 (1990) was performed on the glass substrates for the respective flat panels. Furthermore, the test was performed using a Taber tester (Tdedyne Taber M〇del 5〇3) with the wear wheel fixed at a load of cs·l〇F ’ of 500 g. Further, the turbidity rate after one-time Taber abrasion was measured by a turbidimeter. The rate of change was determined from the turbidity rate before the Taber test. Here, the haze value can be defined as follows by using scattered light (Td) and transmitted light (Tt). Turbidity rate = (Td / Tt) x l00 ° / 〇 Further, the rate of change of turbidity rate (Η) (ΔΗ) can be expressed by the following formula. ΑΗ = turbidity rate after 1000 times of abrasion turbidity rate before H-Taber test Η [Table 1] Sodium tetraborate spray amount (L/m2) 302 gas spray amount (L/m2) Protective film adhesion amount (mg/10 cm square) Number of damage resistance (units/10 cm square) Average boron concentration (at%) Diffusion depth (nm) Helium atom concentration (mol%) Yellowness index wear resistance turbidity change rate ( %) Example 1 0.4 0.1 0.13 25 3.5 40 1.0 3.4 2.5 Example 2 0.4 0.4 0.51 3 3.5 40 1.2 3.5 2.5 Example 3 0.4 1.0 1.35 0 3,5 40 1,8 4.3 2.5 Comparative Example 1 - 0.1 0.1 48 - - 1.6 4.1 4.5 Comparative Example 2 - 0.4 0.1 30 - - 2.5 5.5 4.5 Comparative Example 3 - 1.0 0.5 6 - - 4.3 7.6 4.5 Comparative Example 4 - • * - - - - - 4.5 Comparative Example 5 - - - - - 4.5 - 33·164689.doc 201245058 It can be seen from the results shown in Table 1 that the glass substrates for flat panel displays of Examples 1 to 3 obtained by using tetrasodium oleate have a gas ejection amount of s〇2 compared with Comparative Example 3. If it is equal to or less than the same, it can be kept at the same level or more as the damage, and the yellowness index of the top surface, that is, the Ag colloid color can be suppressed. Further, even if an equivalent amount of sodium sulfate was attached, 31, in Comparative Example i and Comparative Example 2, it was found that the number of scratches on the glass substrate for a flat panel display of Example 1 obtained by using the four-side sodium was small. The reason for this is that the abrasion resistance of the glass substrate itself is improved by being dispersed to the glass substrate. Further, it has been confirmed that the glass substrate for a flat panel of Example 3 is usually washed with water, and the protective film formed on the surface of the glass substrate is removed to exhibit a clean surface. On the other hand, in the glass substrate for a flat panel of Comparative Example 33, even if the water is washed normally, the protective film formed on the surface of the glass substrate cannot be removed and remains. Further, when the film component remaining is measured, it is calcium sulfate and barium sulfate. Further, it is known that the glass substrate for a flat panel of the third embodiment has a turbidity change rate and an improved wear resistance as compared with the glass substrate for a flat panel of Comparative Example 5. The present invention has been described with reference to the specific embodiments of the invention, and the invention may be modified or modified without departing from the spirit and scope of the invention. The present application is hereby incorporated by reference in its entirety in its entirety in its entirety in the the the the the the the the the [Industrial Applicability] 164689.doc • 34· 201245058 According to the present invention, a method for manufacturing a flat panel display mu surface substrate capable of maintaining good scratch resistance and preventing Ag gel color development, and utilizing the same A glass substrate for a flat panel display obtained by the production method. Further, the present invention is not only applicable to a PDP, but also maintains good scratch resistance in the FED, sed, etc., and is suitable for FED, SED, etc., as well as riding and tilting. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a conceptual diagram showing an example of a glass manufacturing line using a floating method. Figure 2 is a cross-sectional view of a large tubular furnace used in the examples. 3 is an explanatory view showing a portion (wearing portion) touched by the abrasion wheel of the Taber test machine used in the evaluation of the scratch resistance, and a measurement portion (measurement portion) of the number of flaws. [Explanation of main component symbols] 1 Dissolving tin 2 is melted Tin bath 3 Melting kiln 4 Melting glass 5 Guide roller 6 Xu cold furnace 11 Large tubular furnace 12 Quartz tube 13 Glass plate for flat panel display 14 Alumina boat

S 1646S9.doc 201245058 15 試劑 16、17 箭頭 18 測試體 19 磨耗部 20 測定部 164689.docS 1646S9.doc 201245058 15 Reagents 16, 17 Arrows 18 Test body 19 Wear parts 20 Measurement department 164689.doc

Claims (1)

201245058 七、申請專利範圍： 1. 一種平面面板顯示器用玻璃基板，其以氧化物為基準且 以質量百分率表示，含有： Si02 : 45〜70%， Al2〇3 : 0〜20%， CaO : 0-20%， Zr02 : 0~13〇/〇， 鹼土金屬氧化物成分之合計量：5〜40%， 鹼金屬氧化物成分之合計量：5〜30%， 至少其中一表面之平均硼濃度為2〜6原子％，且硼自該 表面向内部之擴散深度為20〜80 nm。 2. 如請求項1之平面面板顯示器用玻璃基板，其中上述表 面之自表面起至0.1 μιη之深度為止之平均Η原子濃度為 2.5莫耳％以下。 S 164689.doc201245058 VII. Patent application scope: 1. A glass substrate for flat panel display, which is expressed by mass percentage based on oxide, and contains: Si02: 45~70%, Al2〇3: 0~20%, CaO: 0 -20%, Zr02 : 0~13〇/〇, the total amount of alkaline earth metal oxide components: 5~40%, the total amount of alkali metal oxide components: 5~30%, the average boron concentration of at least one of the surfaces is 2 to 6 atom%, and the diffusion depth of boron from the surface to the inside is 20 to 80 nm. 2. The glass substrate for a flat panel display according to claim 1, wherein an average germanium atom concentration of the surface from a surface to a depth of 0.1 μm is 2.5 mol% or less. S 164689.doc
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